Branched vinyl terminated polymers and methods for production thereof

ABSTRACT

This invention relates to a process for polymerization, comprising (i) contacting, at a temperature greater than 35° C., one or more monomers comprising ethylene and/or propylene, with a catalyst system comprising a metallocene catalyst compound and an activator, (ii) converting at least 50 mol % of the monomer to polyolefin; and (iii) obtaining a branched polyolefin having greater than 50% allyl chain ends, relative to total unsaturated chain ends. The invention also relates to the branched polyolefins and functionalized branched polyolefins.

PRIORITY

This application claims priority to and the benefit of Ser. No.61/467,681, filed Mar. 25, 2011.

FIELD OF THE INVENTION

This invention relates to olefin polymerization, particularly to producevinyl terminated polymers.

BACKGROUND OF THE INVENTION

Alpha-olefins, especially those containing about 6 to about 20 carbonatoms, have been used as intermediates in the manufacture of detergentsor other types of commercial products. Such alpha-olefins have also beenused as comonomers, especially in linear low density polyethylene.Commercially produced alpha-olefins are typically made by oligomerizingethylene. Longer chain alpha-olefins, such as vinyl-terminatedpolyethylenes are also known and can be useful as building blocksfollowing functionalization or as macromonomers.

Allyl terminated low molecular weight solids and liquids of ethylene orpropylene have also been produced, typically for use as branches inpolymerization reactions. See, for example, Rulhoff, Sascha andKaminsky, (“Synthesis and Characterization of Defined BranchedPoly(propylene)s with Different Microstructures by Copolymerization ofPropylene and Linear Ethylene Oligomers (C_(n)=26-28) withMetallocenes/MAO Catalysts,” Macromolecules, 16, 2006, pp. 1450-1460),and Kaneyoshi, Hiromu et al. (“Synthesis of Block and Graft Copolymerswith Linear Polyethylene Segments by Combination of DegenerativeTransfer Coordination Polymerization and Atom Transfer RadicalPolymerization,” Macromolecules, 38, 2005, pp. 5425-5435).

Further, U.S. Pat. No. 4,814,540 discloses bis(pentamethylcyclopentadienyl) hafnium dichloride, bis(pentamethyl cyclopentadienyl)zirconium dichloride and bis(tetramethyl n-butyl cyclopentadienyl)hafnium dichloride with methylalumoxane in toluene or hexane with orwithout hydrogen to make allylic vinyl terminated propylenehomo-oligomers having a low degree of polymerization of 2-10. Theseoligomers do not have high Mns and do not have at least 93% allylicvinyl unsaturation. Likewise, these oligomers lack comonomer and areproduced at low productivities with a large excess of alumoxane (molarratio≧600 Al/M; M=Zr, Hf). Additionally, no less than 60 wt % solvent(solvent+propylene basis) is present in all of the examples.

Teuben, et al. (J. Mol. Catal., 62, 1990, pp. 277-287) discloses the useof [Cp*₂MMe(THT)]+[BPh₄] (M=Zr and Hf; Cp*=pentamethylcyclopentadienyl;Me=methyl, Ph=phenyl; THT=tetrahydrothiophene), to make propyleneoligomers. For M=Zr, a broad product distribution with oligomers up toC₂₄ (number average molecular weight (Mn) of 336) was obtained at roomtemperature. Whereas, for M=Hf, only the dimer 4-methyl-1-pentene andthe trimer 4,6-dimethyl-1-heptene were formed. The dominant terminationmechanism appeared to be beta-methyl transfer from the growing chainback to the metal center, as was demonstrated by deuterium labelingstudies.

X. Yang, et al. (Angew. Chem. Intl Ed. Engl., 31, 1992, pp. 1375)discloses amorphous, low molecular weight polypropylene made at lowtemperatures where the reactions showed low activity and product having90% allylic vinyls, relative to all unsaturations, by ¹H NMR.Thereafter, Resconi, et al. (J. Am. Chem. Soc., 114, 1992, pp.1025-1032), discloses the use ofbis(pentamethylcyclopentadienyl)zirconium andbis(pentamethylcyclopentadienyl)hafnium to polymerize propylene andobtained beta-methyl termination resulting in oligomers and lowmolecular weight polymers with “mainly allyl- and iso-butyl-terminated”chains. As is the case in U.S. Pat. No. 4,814,540, the oligomersproduced do not have at least 93% allyl chain ends, an Mn of about 500to about 20,000 g/mol (as measured by ¹H NMR), and the catalyst has lowproductivity (1-12,620 g/mmol metallocene/hr; >3000 wppm Al inproducts).

Similarly, Small and Brookhart, (Macromolecules, 32, 1999, pp. 2322)disclose the use of a pyridylbisamido iron catalyst in a low temperaturepolymerization to produce low molecular weight amorphous propylenematerials apparently having predominant or exclusive 2,1 chain growth,chain termination via beta-hydride elimination, and high amounts ofvinyl end groups.

Weng et al. (Macromol Rapid Comm. 2000, 21, pp. 1103-1107) disclosesmaterials with up to about 81% vinyl termination made usingdimethylsilyl bis(2-methyl, 4-phenyl-indenyl) zirconium dichloride andmethylalumoxane in toluene at about 120° C. The materials have a Mn ofabout 12,300 (measured with ¹H NMR) and a melting point of about 143° C.

Markel et al. (Macromolecules, 33, 2000, pp. 8541-8548) discloses combbranch-block polyethylene made with Cp₂ZrCl₂ and(C₅Me₄SiMe₂NC₁₂H₂₃)TiCl₂, activated with methyl alumoxane.

Moscardi, et al. (Organometallics, 20, 2001, pp. 1918) discloses the useof rac-dimethylsilylmethylenebis(3-t-butyl indenyl)zirconium dichloridewith methylalumoxane in batch polymerizations of propylene to producematerials where “ . . . allyl end group always prevails over any otherend groups, at any [propene].” In these reactions, morphology controlwas limited and approximately 60% of the chain ends are allylic.

Coates, et al. (Macromolecules, 38, 2005, pp. 6259) disclosespreparation of low molecular weight syndiotactic polypropylene([rrr]=0.46-0.93) with about 100% allyl end groups usingbis(phenoxyimine)titanium dichloride ((PHI)₂TiCl₂) activated withmodified methyl alumoxane (MMAO; Al/Ti molar ratio=200) in batchpolymerizations run between −20° C. and +20° C. for four hours. Forthese polymerizations, propylene was dissolved in toluene to create a1.65 M toluene solution. Catalyst productivity was very low (0.95 to1.14 g/mmol Ti/hr).

JP 2005-336092 A2 discloses the manufacture of vinyl-terminatedpropylene polymers using materials such as H₂SO₄ treatedmontmorillonite, triethylaluminum, triisopropyl aluminum, where theliquid propylene is fed into a catalyst slurry in toluene. This processproduces substantially isotactic macromonomers that do not have asignificant amount of amorphous material.

U.S. Pat. No. 6,897,261 discloses olefin graft copolymers obtained bycopolymerizing an atactic branched macromonomer, wherein themacromonomer is derived from monomers selected from the group consistingof (1) propylene and (2) the combination of propylene and at least oneselected from ethylene, alpha-olefins having from 4 to 20 carbon atoms,cyclic olefins and styrenes, and of which the propylene content fallsbetween 0.1 mol % and 100 mol %, and which macromonomer satisfies thefollowing (a) and (b): (a) its weight-average molecular weight (Mw)measured through gel permeation chromatography (GPC) falls between 400and 200000; (b) its vinyl content is at least 70 mol % of all theunsaturated groups in the macromonomer, wherein the macromonomersatisfies each of the following (i), (ii), and (iii): (i) the ratio ofthe temperature dependency (E₂) of the macromonomer solution viscosityto the temperature dependency (E₁) of the solution viscosity of thelinear polymer which has the same type of monomer, the same chemicalcomposition and the same intrinsic viscosity as those of themacromonomer, E₂/E₁, satisfies the following relationship:1.0<E₂/E₁<2.5.

Rose, et al. (Macromolecules, 41, 2008, pp. 559-567) disclosespoly(ethylene-co-propylene) macromonomers not having significant amountsof iso-butyl chain ends. Those were made with bis(phenoxyimine) titaniumdichloride ((PHI)₂TiCl₂) activated with modified methylalumoxane (MMAO;Al/Ti molar ratio range 150 to 292) in semi-batch polymerizations (30psi propylene added to toluene at 0° C. for 30 min, followed by ethylenegas flow at 32 psi of over-pressure at about 0° C. for polymerizationtimes of 2.3 to 4 hours to produce E-P copolymer having an Mn of about4,800 to 23,300. In four reported copolymerizations, allylic chain endsdecreased with increasing ethylene incorporation roughly according tothe equation:% allylic chain ends(of total unsaturations)=−0.95(mol % ethyleneincorporated)+100.For example, 65% allyl (compared to total unsaturation) was reported forE-P copolymer containing 29 mol % ethylene. This is the highest allylpopulation achieved. For 64 mol % incorporated ethylene, only 42% of theunsaturations are allylic. Productivity of these polymerizations rangedfrom 0.78×10² g/mmol Ti/hr to 4.62×10² g/mmol Ti/hr.

Prior to this work, Zhu, et al. (Macromolecules, 35, 2002, pp.10062-10070 and Macromolecules Rap. Commun, 24, 2003, pp. 311-315)reported only low (−38%) vinyl terminated ethylene-propylene copolymermade with the constrained geometry metallocene catalyst[C₅Me₄(SiMe₂N-tert-butyl)TiMe₂ activated with B(C₆F₅)₃ and MMAO.

Janiak and Blank summarize a variety of work related to oligomerizationof olefins (Macromol. Symp., 236, 2006, pp. 14-22).

U.S. Pat. No. 6,225,432 discloses branched polypropylene compositionswhich have improved melt strength and good processability. The branchedpolypropylene compositions have a polydispersity of less than 4.0 and amelt point greater than 90° C. The weight average branching index g ofthe polypropylene compositions is less than 0.95.

However, processes to make branched polyolefins having high amounts ofallyl terminations on a commercial scale are not known. Accordingly,there is a need for new processes that produce allyl terminated branchedpolyolefins that have allyl termination present in high amounts (50% ormore), particularly in high yields and with a wide range of molecularweights, that can be made at commercial rates (5,000 g/mmol/hrproductivity or more). There is further a need for branched polyolefinreactive materials having high amounts of allyl termination which can befunctionalized and used in additive applications or as blendingcomponents.

SUMMARY OF THE INVENTION

The invention relates to processes for polymerization, comprising:

(i) contacting, preferably at a temperature greater than 35° C., one ormore monomers comprising ethylene and/or propylene, with a catalystsystem comprising a metallocene catalyst compound and an activator,wherein the metallocene catalyst compound is represented by thefollowing formula:

whereM is selected from the group consisting of zirconium or hafnium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines,ethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system);each R¹, R², R³, R⁴, R⁵, and R⁶, is, independently, hydrogen or asubstituted or unsubstituted hydrocarbyl group, a heteroatom orheteroatom containing group;further provided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated; andfurther provided that any of adjacent R⁴, R⁵, and R⁶ groups may form afused ring or multicenter fused ring system where the rings may bearomatic, partially saturated or saturated;T is a bridging group represented by the formula R₂ ^(a)J, where J isone or more of C, Si, Ge, N, or P, and each R^(a) is, independently,hydrogen, halogen, C₁ to C₂₀ hydrocarbyl or a C₁ to C₂₀ substitutedhydrocarbyl,provided that at least one R³ is a substituted or unsubstituted phenylgroup, if any of R¹, R², R⁴, R⁵ or R⁶ are not hydrogen;(ii) preferably converting at least 50 mol % of the monomer topolyolefin; and(iii) obtaining a branched polyolefin having greater than 50% allylchain ends, relative to total unsaturated chain ends and a Tm of 60° C.or more.

This invention also relates to a branched polyolefin having an Mn (¹HNMR) of 7,500 to 60,000 g/mol comprising one or more alpha olefinderived units comprising ethylene and/or propylene, and having:

(i) 50% or greater allyl chain ends, relative to total number ofunsaturated chain ends; and

(ii) a g′ vis of 0.90 or less.

This invention also relates to branched polyolefins having an Mn (GPC)greater than 60,000 g/mol comprising one or more alpha olefinscomprising ethylene and/or propylene, and having: (i) 50% or greaterallyl chain ends, relative to total unsaturated chain ends; (ii) a g′vis of 0.90 or less; and optionally; and (iii) a bromine number which,upon complete hydrogenation, decreases by at least 50%.

The invention further relates to branched polyolefins having an Mn (¹HNMR) of less than 7,500 g/mol comprising one or more alpha olefinderived units comprising ethylene and/or propylene, and having:

(i) a ratio of percentage of saturated chain ends to percentage of allylchain ends of 1.2 to 2.0; and

(ii) 50% or greater allyl chain ends, relative to total moles ofunsaturated chain ends.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of the relationship between g′ vis and log Mw for allylterminated branched polypropylene polymers made with MetalloceneA/Activator III (Examples, Table 3, Runs 59-65).

DETAILED DESCRIPTION

The inventors have surprisingly discovered new processes to makebranched polyolefins having high amounts of allyl terminations. Thesenew processes can be run under commercial conditions and are capable ofproducing the branched polyolefins at commercial rates. Furthermore,these processes are typically run using non-coordinating anionactivators, preferably bulky activators, as defined below.

Described herein are such processes to produce the branched polyolefins,the branched olefin products, and compositions comprising such branchedpolyolefins. “Branched” as used herein, means a polyolefin having a g′vis of 0.90 or less, or if the polyolefin has a Mn (¹H MNR) of less than7,500 g/mol, the branched polyolefin has a ratio of saturated chain endsto percentage of allyl chain ends of 1.2 to 2.0. These branchedpolyolefins having high amounts of allyl chain ends may find utility asmacromonomers for the synthesis of branched poly(macromonomers), blockcopolymers, and as additives, for example, as additives to, or blendingagents in, lubricants, waxes, and adhesives. Advantageously, when usedas an additive, such as to film compositions, the branched nature ofthese polyolefins may improve the desired mechanical properties byallowing optimal thermoforming and molding at lower temperatures,thereby reducing energy consumption of the film forming process, ascompared to linear polyolefin analogues. Further advantageously, thehigh amounts of allyl chain ends of these branched polyolefins providesa facile path to functionalization. The functionalized branchedpolyolefins may be also useful as additives or blending agents.

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as in CHEMICALAND ENGINEERING NEWS, 63(5), page 27, (1985). Therefore, a “Group 4metal” is an element from Group 4 of the Periodic Table.

“Catalyst productivity” is a measure of how many kilograms of polymer(P) are produced using a polymerization catalyst comprising W moles ofcatalyst (W); and may be expressed in units of kilograms of polymer permole of catalyst.

Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor.

Catalyst activity is a measure of how active the catalyst is and isreported as the mass of product polymer (P) produced per kg of catalyst(cat) used (kgP/kgcat).

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, including, but not limited to ethylene, propylene, and butene,the olefin present in such polymer or copolymer is the polymerized formof the olefin. For example, when a copolymer is said to have an“ethylene” content of 35 wt % to 55 wt %, it is understood that the merunit in the copolymer is derived from ethylene in the polymerizationreaction and said derived units are present at 35 wt % to 55 wt %, basedupon the weight of the copolymer. A “polymer” has two or more of thesame or different mer units. The term “polymer,” as used herein,includes oligomers (up to 100 mer units), and larger polymers (greaterthan 100 mer units). A “homopolymer” is a polymer having mer units thatare the same. A “copolymer” is a polymer having two or more mer unitsthat are different from each other. A “terpolymer” is a polymer havingthree mer units that are different from each other. “Different” as usedto refer to mer units indicates that the mer units differ from eachother by at least one atom or are different isomerically. Accordingly,the definition of copolymer, as used herein, includes terpolymers andthe like.

As used herein, Mn is number average molecular weight (measured by ¹HNMR, unless stated otherwise), Mw is weight average molecular weight(measured by Gel Permeation Chromatography, GPC), and Mz is z averagemolecular weight (measured by GPC), wt % is weight percent, mol % ismole percent, vol % is volume percent and mol is mole. Molecular weightdistribution (MWD) is defined to be Mw divided by Mn (measured by GPC),Mw/Mn. Unless otherwise noted, all molecular weights (e.g., Mw, Mn, Mz)have units of g/mol. Also, room temperature is 23° C. unless otherwisenoted.

Bromine number is determined by ASTM D 1159.

Processes for Making Vinyl Terminated Branched Polyolefins

This invention relates to a process for polymerization, comprising:

(i) contacting, preferably at a temperature greater than 35° C.,preferably in the range of from about 35 to 150° C., from 40 to 140° C.,from 60 to 140° C., or from 80 to 130° C., one or more monomerscomprising ethylene and/or propylene (preferably propylene) and,optionally, one or more C₄ to C₄₀ alpha olefin monomers (preferablybutene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene,cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof), with acatalyst system capable of producing a branched polyolefin having allylchain ends, the catalyst system comprising a metallocene catalystcompound and an activator, wherein the metallocene catalyst compound isrepresented by the following formula:

where:M is selected from the group consisting of zirconium or hafnium(preferably hafnium);each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines,ethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system) (preferably X is a halide or a hydrocarbylradical having from 1 to 20 carbon atoms, preferably X is chloride ormethyl);each R¹, R², R³, R⁴, R⁵, and R⁶, is, independently, hydrogen or asubstituted or unsubstituted hydrocarbyl group, a heteroatom orheteroatom containing group;further provided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated; andfurther provided that any of adjacent R⁴, R⁵, and R⁶ groups may form afused ring or multicenter fused ring system where the rings may bearomatic, partially saturated or saturated;T is a bridging group represented by the formula R₂ ^(a)J, where J isone or more of C, Si, Ge, N, or P (preferably J is Si), and each R^(a)is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl or a C₁ toC₂₀ substituted hydrocarbyl (preferably R^(a) is methyl, ethyl,chloride), provided that at least one R³, preferably both, are asubstituted or unsubstituted phenyl group, if any of R¹, R², R⁴, R⁵ orR⁶ are not hydrogen;(ii) preferably converting at least 50 mol % of the monomer topolyolefin, more preferably at least 60 mol %, at least 70 mol %, atleast 80 mol %; and(iii) obtaining a branched polyolefin having greater than 50% allylchain ends, relative to total unsaturated chain ends (preferably 60% ormore, preferably 70% or more, preferably 80% or more, preferably 90% ormore, preferably 95% or more) and a Tm of 60° C. or more (preferably100° C. or more, preferably 120° C. or more).

The inventive processes described herein are run at commercial rates. Insome embodiments, the productivity is 4500 g/mmol or more, preferably5000 g/mmol or more, preferably 10,000 g/mmol or more, preferably 50,000g/mmol or more. In other embodiments, the productivity is at least80,000 g/mmol, preferably at least 150,000 g/mmol, preferably at least200,000 g/mmol, preferably at least 250,000 g/mmol, preferably at least300,000 g/mmol

In an alternate embodiment, the activity of the catalyst is at least10,000 kg polymer per kg catalyst, preferably 50,000 or more kg polymerper kg catalyst, preferably 100,000 or more kg polymer per kg catalyst,preferably 150,000 or more kg polymer per kg catalyst.

In an alternate embodiment, the conversion of olefin monomer is at least50 mol %, based upon the weight of the monomer entering the reactionzone, preferably 60 mol % or more, preferably 70 mol % or more,preferably 80 mol % or more.

The inventive processes described herein can be run at temperatures andpressures suitable for commercial production of these branched vinylterminated polymers. Typical temperatures and/or pressures include atemperature greater than 35° C. (preferably in the range of from about35 to 150° C., from 40 to 140° C., from 60 to 140° C., or from 80 to130° C.) and a pressure in the range of from about 0.35 to 10 MPa(preferably from 0.45 to 6 MPa or from 0.5 to 4 MPa).

The inventive processes described herein have a residence time suitablefor commercial production of these branched vinyl terminated polymers.In a typical polymerization, the residence time of the polymerizationprocess is up to 300 minutes, preferably in the range of from about 1 to300 minutes, preferably from 5 to 250 minutes, preferably from about 10to 120 minutes, or preferably from about 10 to 60 minutes.

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof, such as can be foundcommercially (Isopar™); and perhalogenated hydrocarbons such asperfluorinated C₄₋₁₀ alkanes. Suitable solvents also include liquidolefins which may act as monomers or comonomers including ethylene,propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In apreferred embodiment, aliphatic hydrocarbons are used as the solvent,such as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In another embodiment, thesolvent is not aromatic, preferably aromatics are present in the solventat less than 1 wt %, preferably at 0.5 wt %, preferably at 0 wt % basedupon the weight of the solvents.

In a preferred embodiment, the feed concentration for the polymerizationis 60 vol % solvent or less, preferably 40 vol % or less, or preferably20 vol % or less, preferably 0 vol % based on the total volume of thefeedstream. Preferably the polymerization is run in a bulk process.

In some embodiments, where butene is the comonomer, the butene sourcemay be a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example C₄ raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

Processes of this invention can be carried out in any manner known inthe art. Any suspension, homogeneous bulk, solution, slurry, or gasphase polymerization process known in the art can be used. Suchprocesses can be run in a batch, semi-batch, or continuous mode.Homogeneous polymerization processes and slurry are preferred. (Ahomogeneous polymerization process is defined to be a process where atleast 90 wt % of the product is soluble in the reaction media.) A bulkhomogeneous process is particularly preferred. (A bulk process isdefined to be a process where monomer concentration in all feeds to thereactor is 70 vol % or more.) Alternately, no solvent or diluent ispresent or added in the reaction medium, (except for the small amountsused as the carrier for the catalyst system or other additives, oramounts typically found with the monomer; e.g., propane in propylene).Preferably, the process is a single stage polymerization process. Inanother embodiment, the process is a slurry process. As used herein theterm “slurry polymerization process” means a polymerization processwhere a supported catalyst is employed and monomers are polymerized onthe supported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent). By “continuous mode” is meantthat there is continuous addition to, and withdrawal of reactants andproducts from, the reactor system. Continuous processes can be operatedin steady state; i.e., the composition of effluent remains fixed withtime if the flow rate, temperature/pressure and feed composition remaininvariant. For example, a continuous process to produce a polymer wouldbe one where the reactants are continuously introduced into one or morereactors and polymer product is continuously withdrawn.

In a preferred embodiment hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa),preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1to 10 psig (0.7 to 70 kPa). It has been found that in the presentsystems, hydrogen can be used to provide increased activity withoutsignificantly impairing the catalyst's ability to produce allylic chainends. Preferably the catalyst activity (calculated as g/mmolcatalyst/hr) is at least 20% higher than the same reaction withouthydrogen present, preferably at least 50% higher, preferably at least100% higher.

Useful reaction vessels include reactors (including continuous stirredtank reactors, batch reactors, reactive extruder, pipe or pump. A“reaction zone” also referred to as a “polymerization zone” is definedas an area where activated catalysts and monomers are contacted and apolymerization reaction takes place. When multiple reactors are used ineither series or parallel configuration, each reactor is considered as aseparate polymerization zone. For a multi-stage polymerization in both abatch reactor and a continuous reactor, each polymerization stage isconsidered as a separate polymerization zone. In a preferred embodiment,the polymerization described herein occurs within a single reactionzone. Alternately the polymerization described herein may occur inmultiple reaction zones.

In a preferred embodiment hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa),preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1to 10 psig (0.7 to 70 kPa). It has been found that in the presentsystems, hydrogen can be used to provide increased activity withoutsignificantly impairing the catalyst's ability to produce allylic chainends. Preferably the catalyst activity (calculated as g/mmolcatalyst/hr) is at least 20% higher than the same reaction withouthydrogen present, preferably at least 50% higher, preferably at least100% higher.

In a preferred embodiment, little or no alumoxane is used in the processto produce the vinyl terminated polymers. Preferably, alumoxane ispresent at zero mol %, alternately the alumoxane is present at a molarratio of aluminum to transition metal less than 500:1, preferably lessthan 300:1, preferably less than 100:1, preferably less than 1:1.

In an alternate embodiment, if an alumoxane is used to produce the vinylterminated polymers, then the alumoxane has been treated to remove freealkyl aluminum compounds, particularly trimethyl aluminum.

Further, in a preferred embodiment, the activator used herein to producethe vinyl terminated polymer is a bulky activator as defined herein andis discrete.

In a preferred embodiment, little or no scavenger is used in the processto produce the vinyl terminated polymers. Preferably, scavenger (such astri alkyl aluminum) is present at zero mol %, alternately the scavengeris present at a molar ratio of scavenger metal to transition metal ofless than 100:1, preferably less than 50:1, preferably less than 15:1,preferably less than 10:1.

In a preferred embodiment, the polymerization: 1) is conducted attemperatures of 0 to 300° C. (preferably 25 to 150° C., preferably 40 to120° C., preferably 45 to 80° C.); 2) is conducted at a pressure ofatmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferablyfrom 0.45 to 6 MPa, preferably from 0.5 to 4 MPa); 3) is conducted in analiphatic hydrocarbon solvent (such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; preferably where aromatics are present in the solvent at lessthan 1 wt %, preferably at 0.5 wt %, preferably at 0 wt % based upon theweight of the solvents); 4) wherein the catalyst system used in thepolymerization comprises less than 0.5 mol %, preferably 0 mol %alumoxane, alternately the alumoxane is present at a molar ratio ofaluminum to transition metal less than 500:1, preferably less than300:1, preferably less than 100:1, preferably less than 1:1); 5) thepolymerization occurs in one reaction zone; 6) the productivity of thecatalyst compound is at least 80,000 g/mmol (preferably at least 150,000g/mmol, preferably at least 200,000 g/mmol, preferably at least 250,000g/mmol, preferably at least 300,000 g/mmol); 7) optionally scavengers(such as trialkyl aluminum compounds) are absent (e.g., present at zeromol %, alternately the scavenger is present at a molar ratio ofscavenger metal to transition metal of less than 100:1, preferably lessthan 50:1, preferably less than 15:1, preferably less than 10:1); and 8)optionally hydrogen is present in the polymerization reactor at apartial pressure of 0.001 to 50 psig (0.007 to 345 kPa) (preferably from0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7to 70 kPa)). In a preferred embodiment, the catalyst system used in thepolymerization comprises no more than one catalyst compound. A “reactionzone” also referred to as a “polymerization zone” is a vessel wherepolymerization takes place, for example a batch reactor. When multiplereactors are used in either series or parallel configuration, eachreactor is considered as a separate polymerization zone. For amulti-stage polymerization in both a batch reactor and a continuousreactor, each polymerization stage is considered as a separatepolymerization zone. In a preferred embodiment, the polymerizationoccurs in one reaction zone. Room temperature is 23° C. unless otherwisenoted.

Catalyst Systems

In embodiments herein, the invention relates to processes for makingvinyl terminated branched polyolefins at commercial rates and undercommercial conditions, wherein the process comprises contacting themonomers in the presence of a catalyst system comprising a metallocenecatalyst compound and an activator capable of producing branchedpolyolefins having 50% or more allyl chain ends. It is within the scopeof this invention that the catalyst system is a mixed catalyst systemcomprising one or more non-metallocene catalyst compounds, one or moremetallocene catalyst compounds, or a combination thereof, preferably themixed catalyst system comprises two or more metallocene catalystcompounds. Preferably, the catalyst system is a single catalyst system.Likewise one, two, or more activators may be used in the catalystsystem.

In the description herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, a catalyst compound, or a transitionmetal compound, and these terms are used interchangeably. Apolymerization catalyst system is a catalyst system that can polymerizemonomers to polymer. A “catalyst system” is a combination of at leastone catalyst compound, at least one activator, an optional co-activator,and an optional support material. An “anionic ligand” is a negativelycharged ligand which donates one or more pairs of electrons to a metalion. A “neutral donor ligand” is a neutrally charged ligand whichdonates one or more pairs of electrons to a metal ion.

For the purposes of this invention and the claims thereto, when catalystsystems are described as comprising neutral stable forms of thecomponents, it is well understood by one of ordinary skill in the art,that the ionic form of the component is the form that reacts with themonomers to produce polymers.

A metallocene catalyst is defined as an organometallic compound with atleast one π-bound cyclopentadienyl moiety (or substitutedcyclopentadienyl moiety) and more frequently two π-boundcyclopentadienyl-moieties or substituted moieties. This includes otherπ-bound moieties such as indenyls or fluorenyls or derivatives thereof.

The metallocene, activator, optional co-activator, and optional supportcomponents of the particularly useful catalyst systems are discussedbelow.

(a) Metallocene Catalyst Compound

A “hydrocarbyl” is a radical made of hydrogen and carbon. The term“substituted” means that a hydrogen group has been replaced with ahydrocarbyl group, a heteroatom, or a heteroatom containing group. Forexample, methyl cyclopentadiene (Cp) is a Cp group substituted with amethyl group, ethyl alcohol is an ethyl group substituted with an —OHgroup, and a “substituted hydrocarbyl” is a radical made of carbon andhydrogen where at least one hydrogen is replaced by a heteroatom.

For purposes of this invention and claims thereto, “alkoxides” includethose where the alkyl group is a C₁ to C₄₀ hydrocarbyl. The alkyl groupmay be straight chain, branched, or cyclic. The alkyl group may besaturated or unsaturated. In some embodiments, the alkyl group maycomprise at least one aromatic group.

The metallocene catalyst compound of the catalyst system is representedby the formula:

whereM is selected from the group consisting of zirconium or hafnium(preferably hafnium);each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines,ethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system) (preferably X is a halide or a hydrocarbylradical having from 1 to 20 carbon atoms, preferably X is chloride ormethyl);each R¹, R², R³, R⁴, R⁵, and R⁶, is, independently, hydrogen or asubstituted or unsubstituted hydrocarbyl group, a heteroatom orheteroatom containing group;further provided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated;further provided that any of adjacent R⁴, R⁵, and R⁶ groups may form afused ring or multicenter fused ring system where the rings may bearomatic, partially saturated or saturated; andT is a bridging group represented by the formula R₂ ^(a)J, where J isone or more of C, Si, Ge, N, or P (preferably J is Si), and each R^(a)is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl or a C₁ toC₂₀ substituted hydrocarbyl, (preferably R^(a) is methyl, ethyl,chloride), provided that at least one R³, preferably both, are asubstituted or unsubstituted phenyl group, if any of R¹, R², R⁴, R⁵ orR⁶ are not hydrogen;

Particularly preferred R^(a) substituent groups include a C₁ to C₂₀hydrocarbyls, such as methyl, ethyl, propyl (including isopropyl,sec-propyl), butyl (including t-butyl and sec-butyl), neopentyl,cyclopentyl, hexyl, octyl, nonyl, decyl, phenyl, substituted phenyl,benzyl (including substituted benzyl), cyclohexyl, cyclododecyl,norbornyl, and all isomers thereof.

Examples of bridging group R₂ ^(a)T useful herein may be represented byR′₂C, R′₂Si, R′₂Ge, R′₂CCR′₂, R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′,R′C═CR′CR′₂, R′₂CCR′═CR′CR′₂, R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂,R′₂CSiR′₂, R′₂SiSiR′₂, R₂CSiR′₂CR′₂, R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂,R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂, R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂,R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂, R′₂C—O—CR′₂,R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂, R′₂C—O—CR′═CR′, R′₂C—S—CR′₂,R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′, R′₂C—Se—CR′₂,R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR₂CR′₂, R′₂C—Se—CR′═CR′, R′₂C—N═CR′,R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′,R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, and R′₂C—PR′—CR′₂ where R′ ishydrogen or a C₁-C₂₀ containing hydrocarbyl or substituted hydrocarbyl.Preferably, the bridging group R₂ ^(a)T comprises carbon or silica, suchas dialkylsilyl, preferably the bridging group is selected from CH₂,CH₂CH₂, C(CH₃)₂, SiMe₂, SiPh₂, SiMePh, and (Ph)₂C.

Catalyst compounds that are particularly useful in this inventioninclude one or more of:

-   rac-dimethylsilylbis(indenyl)hafnium dimethyl,-   rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl,-   dimethyl    rac-dimethylsilyl-bis(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)hafnium    dimethyl, and-   rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl.

In an alternate embodiment, the “dimethyl” after the transition metal inthe list of catalyst compounds above is replaced with a dihalide (suchas dichloride or difluoride) or a bisphenoxide.

In an alternate embodiment, “hafnium” in the list of catalyst compoundsabove is replaced with zirconium. In an alternate embodiment,“zirconium” in the list of catalyst compounds above is replaced withhafnium.

(b) Activator

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include ionizing activators, whichmay be neutral or ionic, and conventional-type cocatalysts. Preferredactivators typically include ionizing anion precursor compounds thatabstract one reactive, σ-bound, metal ligand making the metal complexcationic and providing a charge-balancing noncoordinating or weaklycoordinating anion.

Preferably, little or no alumoxane is used in the process to produce thebranched polyolefins. Preferably, alumoxane is present at zero mol %,alternately the alumoxane is present at a molar ratio of aluminum totransition metal less than 500:1, preferably less than 300:1, preferablyless than 100:1, preferably less than 1:1. In an alternate embodiment,if an alumoxane is used to produce the branched polyolefins then, thealumoxane has been treated to remove free alkyl aluminum compounds,particularly trimethyl aluminum.

Preferably a non-alumoxane is used as the activator. Further, in apreferred embodiment, the activator used herein to produce the branchedpolyolefins is bulky as defined herein and is discrete.

Ionizing Activators

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis(pentafluorophenyl) borate, a tris perfluorophenylboron metalloid precursor or a tris perfluoronapthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459) or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators. Muchpreferred activators are the ionic ones, not the neutral boranes.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium, or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogens, substituted alkyls, aryls, arylhalides, alkoxy, andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl, ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is tris perfluorophenyl boron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP 0 570982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A;EP 0 277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741;5,206,197; 5,241,025; 5,384,299; 5,502,124; and U.S. patent applicationSer. No. 08/285,380, filed Aug. 3, 1994, all of which are herein fullyincorporated by reference.

Ionic catalysts can be prepared by reacting a transition metal compoundwith some neutral Lewis acids, such as B(C₆F₆)₃, which upon reactionwith the hydrolyzable ligand (X) of the transition metal compound formsan anion, such as ([B(C₆F₅)₃(X)]⁻), which stabilizes the cationictransition metal species generated by the reaction. The catalysts canbe, and preferably are, prepared with activator components which areionic compounds or compositions.

Compounds useful as an activator component in the preparation of theionic catalyst systems used in the process of this invention comprise acation, which is preferably a Bronsted acid capable of donating aproton, and a compatible non-coordinating anion which anion isrelatively large (bulky), capable of stabilizing the active catalystspecies (the Group 4 cation) which is formed when the two compounds arecombined and said anion will be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated substrates or otherneutral Lewis bases such as ethers, amines and the like. Two classes ofcompatible non-coordinating anions have been disclosed in EP 0 277,003 Aand EP 0 277,004 A published 1988: 1) anionic coordination complexescomprising a plurality of lipophilic radicals covalently coordinated toand shielding a central charge-bearing metal or metalloid core; and 2)anions comprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L-H)_(d) ⁺(A^(d−))  (14)wherein L is a neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronstedacid; A^(d−) is a non-coordinating anion having the charge d−; and d is1, 2, or 3.

The cation component, (L-H)_(d) ⁺ may include Bronsted acids such asprotonated Lewis bases capable of protonating a moiety, such as an alkylor aryl, from the bulky ligand metallocene containing transition metalcatalyst precursor, resulting in a cationic transition metal species.

The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such asdimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 2, 3, 4, 5, or 6;n−k=d; M is an element selected from Group 13 of the Periodic Table ofthe Elements, preferably boron or aluminum, and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having upto 20 carbon atoms with the proviso that in not more than 1 occurrenceis Q a halide. Preferably, each Q is a fluorinated hydrocarbyl grouphaving 1 to 20 carbon atoms, more preferably each Q is a fluorinatedaryl group, and most preferably each Q is a pentafluoryl aryl group.Examples of suitable A^(d−) also include diboron compounds as disclosedin U.S. Pat. No. 5,447,895, which is fully incorporated herein byreference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in the preparation of the catalystsystem of the processes of this invention are tri-substituted ammoniumsalts, such as:

trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, anddialkyl ammonium salts, such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and additional tri-substitutedphosphonium salts, such as tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Most preferably, the ionic stoichiometric activator (L-H)_(d) ⁺ (A^(d−))is, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetrakis(perfluorophenyl)borate.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing a bulky ligandmetallocene catalyst cation and their non-coordinating anion are alsocontemplated, and are described in EP 0 426 637 A, EP 0 573 403 A, andU.S. Pat. No. 5,387,568, which are all herein incorporated by reference.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to said cation or which is only weakly coordinated tosaid cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral fourcoordinate metallocene compound and a neutral by-product from the anion.Non-coordinating anions useful in accordance with this invention arethose that are compatible, stabilize the metallocene cation in the senseof balancing its ionic charge at +1, yet retain sufficient lability topermit displacement by an ethylenically or acetylenically unsaturatedmonomer during polymerization. In addition to these activator compoundsor co-catalysts, scavengers are used such as tri-isobutyl aluminum ortri-octyl aluminum. Preferably, the activator is a non-coordinatinganion activator.

Inventive processes also can employ cocatalyst compounds or activatorcompounds that are initially neutral Lewis acids but form a cationicmetal complex and a noncoordinating anion, or a zwitterionic complexupon reaction with the invention compounds. For example,tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbylor hydride ligand to yield an invention cationic metal complex andstabilizing noncoordinating anion, see EP 0 427 697 A and EP 0 520 732 Afor illustrations of analogous Group-4 metallocene compounds. Also, seethe methods and compounds of EP 0 495 375 A. For formation ofzwitterionic complexes using analogous Group 4 compounds, see U.S. Pat.Nos. 5,624,878; 5,486,632; and 5,527,929.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(OX^(e+))_(d)(A^(d−))_(e)  (16)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; and A^(d−) is a non-coordinating anion having the charged−; and d is 1 2, or 3. Examples of cationic oxidizing agents include:ferrocenium, hydrocarbyl-substituted ferrocenium, Ag+ or Pb+². Preferredembodiments of A^(d−) are those anions previously defined with respectto the Bronsted acid containing activators, especiallytetrakis(pentafluorophenyl)borate.

The typical NCA (or non-alumoxane activator) activator-to-catalyst ratiois a 1:1 molar ratio. Alternate preferred ranges include from 0.1:1 to100:1, alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1,alternately from 1:1 to 1000:1. A particularly useful range is from0.5:1 to 10:1, preferably 1:1 to 5:1.

Bulky Activators

The inventors have surprisingly found that bulky activators areparticularly useful. Bulky activators can advantageously produce higherMw, higher Tm, and/or a greater amount of allyl chain ends than the samecatalyst with a non-bulky activator, under the same polymerizationconditions.

“Bulky activator” as used herein refers to anionic activatorsrepresented by the formula:

whereeach R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ canform one or more saturated or unsaturated, substituted or unsubstitutedrings (preferably R₂ and R₃ form a perfluorinated phenyl ring);L is an neutral Lewis base;(L-H)⁺ is a Bronsted acid;d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3V_(S), here V_(S) is the scaledvolume. V_(S) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(S) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

Structure of boron Molecular Formula of MV Total MV Activatorsubstituents each substituent V_(s) (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoronaphthyl) borate

C₁₀F₇ 34 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl) borate

C₁₂F₉ 42 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 62 515 2060

Exemplary bulky activators useful in catalyst systems herein include:trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], and the types disclosed in U.S.Pat. No. 7,297,653.

It is within the scope of this invention that catalyst compounds can becombined with one or more activators or activation methods describedabove.

(iii) Optional Co-Activators and Scavengers

In addition to these activator compounds, scavengers or co-activatorsmay be used. Aluminum alkyl or organoaluminum compounds which may beutilized as co-activators (or scavengers) include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, and tri-n-octylaluminum.

(iv) Optional Support Materials

In embodiments herein, the catalyst system may comprise an inert supportmaterial. Preferably, the supported material is a porous supportmaterial, for example, talc, and inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other organic orinorganic support material, and the like, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in metallocenecatalyst systems herein include Groups 2, 4, 13, and 14 metal oxidessuch as silica, alumina, and mixtures thereof. Other inorganic oxidesthat may be employed either alone or in combination with the silica, oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, for example, finely dividedfunctionalized polyolefins such as finely divided polyethylene.Particularly useful supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania and the like. Preferredsupport materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof,more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 μm.Most preferably the surface area of the support material is in the rangeof from about 100 to about 400 m²/g, pore volume from about 0.8 to about3.0 cc/g and average particle size is from about 5 to about 100 μm. Theaverage pore size of the support material useful in the invention is inthe range of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å. In some embodiments, the support materialis a high surface area, amorphous silica (surface area=300 m²/gm; porevolume of 1.65 cm³/gm), examples of which are marketed under thetradenames of DAVISON 952 or DAVISON 955 by the Davison ChemicalDivision of W.R. Grace and Company. In other embodiments, DAVISON 948 isused.

The support material should be dry, that is, free of absorbed water.Drying of the support material can be effected by heating or calciningat about 100° C. to about 1000° C., preferably at least about 600° C.When the support material is silica, it is heated to at least 200° C.,preferably about 200° C. to about 850° C., and most preferably at about600° C.; and for a time of about 1 minute to about 100 hours, from about12 hours to about 72 hours, or from about 24 hours to about 60 hours.The calcined support material must have at least some reactive hydroxyl(OH) groups to produce the catalyst system of this invention. Thecalcined support material is then contacted with at least onepolymerization catalyst comprising at least one metallocene compound andan activator.

Methods of Making the Supported Catalyst Systems

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a metallocene compound and an activator.The slurry of the support material in the solvent is prepared byintroducing the support material into the solvent, and heating themixture to about 0 to about 70° C., preferably to about 25 to about 60°C., preferably at room temperature. Contact times typically range fromabout 0.5 hours to about 24 hours, from about 0.5 hours to about 8hours, or from about 0.5 hours to about 4 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator, and the metallocene compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene and ethylbenzene, may also be employed.

In embodiments herein, the support material is contacted with a solutionof a metallocene compound and an activator, such that the reactivegroups on the support material are titrated, to form a supportedpolymerization catalyst. The period of time for contact between themetallocene compound, the activator, and the support material is as longas is necessary to titrate the reactive groups on the support material.To “titrate” is meant to react with available reactive groups on thesurface of the support material, thereby reducing the surface hydroxylgroups by at least 80%, at least 90%, at least 95%, or at least 98%. Thesurface reactive group concentration may be determined based on thecalcining temperature and the type of support material used. The supportmaterial calcining temperature affects the number of surface reactivegroups on the support material available to react with the metallocenecompound and an activator: the higher the drying temperature, the lowerthe number of sites. For example, where the support material is silicawhich, prior to the use thereof in the first catalyst system synthesisstep, is dehydrated by fluidizing it with nitrogen and heating at about600° C. for about 16 hours, a surface hydroxyl group concentration ofabout 0.7 millimoles per gram (mmols/gm) is typically achieved. Thus,the exact molar ratio of the activator to the surface reactive groups onthe carrier will vary. Preferably, this is determined on a case-by-casebasis to assure that only so much of the activator is added to thesolution as will be deposited onto the support material without leavingexcess of the activator in the solution.

The amount of the activator which will be deposited onto the supportmaterial without leaving excess in the solution can be determined in anyconventional manner, e.g., by adding the activator to the slurry of thecarrier in the solvent, while stirring the slurry, until the activatoris detected as a solution in the solvent by any technique known in theart, such as by ¹H NMR. For example, for the silica support materialheated at about 600° C., the amount of the activator added to the slurryis such that the molar ratio of B to the hydroxyl groups (OH) on thesilica is about 0.5:1 to about 4:1, preferably about 0.8:1 to about 3:1,more preferably about 0.9:1 to about 2:1 and most preferably about 1:1.The amount of boron on the silica may be determined by using ICPES(Inductively Coupled Plasma Emission Spectrometry), which is describedin J. W. Olesik, “Inductively Coupled Plasma-Optical EmissionSpectroscopy,” in the Encyclopedia of Materials Characterization, C. R.Brundle, C. A. Evans, Jr. and S. Wilson, Eds., Butterworth-Heinemann,Boston, Mass., 1992, pp. 633-644. In another embodiment, it is alsopossible to add such an amount of activator which is in excess of thatwhich will be deposited onto the support, and then remove, e.g., byfiltration and washing, any excess of the activator.

Vinyl Terminated Branched Polyolefins

Embodiments herein relate to branched polyolefins having allyl chainends of 50% or more. The inventors have surprisingly found that theprocesses disclosed herein give rise to an increased population of longchain branched products, possibly through vinyl macromonomerre-incorporation. Without wishing to be bound by theory, the inventorsopine that the branching is likely of the “T” variety, and thesebranched polyolefins retain high amounts of allyl chain ends.

The branched polyolefins having 50% or more allyl chain ends produced bythe processes disclosed herein is:

(a) branched, having at least one of:

(i) a branching index (g′ vis) of less than 0.90 (preferably 0.85 orless, preferably 0.80 or less); or

(ii) a ratio of percentage of saturated chain ends (preferably isobutylchain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably1.6 to 1.8), wherein the percentage of saturated chain ends isdetermined using ¹³C NMR as described in WO 2009/155471 at paragraph[0095] and [0096] except that the spectra are referenced to the chemicalshift of the solvent, tetrachloroethane-d₂; or

(iii) a ratio of Mn(GPC)/Mn(¹H NMR) of 0.95 or less (preferably 0.90 orless, preferably 0.85 or less, preferably 0.80 or less); and

(b) has at least 50% allyl chain ends, relative to total unsaturatedchain ends (preferably 60% or more, preferably 70% or more, preferably75% or more, preferably 80% or more, preferably 90% or more, preferably95% or more) and having at least one of:

(i) a bromine number which, upon complete hydrogenation, decreases by atleast 50% (preferably at least 75%); or

(ii) an allyl chain end to internal vinylidene ratio of greater than 5:1(preferably greater than 10:1); or

(iii) an allyl chain end to vinylidene chain end ratio of greater than10:1 (preferably greater than 15:1), or

(iv) an allyl chain end to vinylene chain end ratio of greater than 1:1(preferably greater than 2:1, greater than 5:1, or greater than 10:1).

With respect to branching, in embodiments where the branched polyolefinshave an Mn (measured by ¹H NMR) of 7,500 to 60,000 g/mol, the branchedpolyolefin has:

(i) a branching index (g′ vis) of less than 0.90 (preferably less than0.85, less than 0.80, or less than 0.75); and/or

(ii) a ratio of percentage of saturated chain ends (preferably isobutylchain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably1.6 to 1.8), wherein the percentage of saturated chain ends isdetermined using ¹³C NMR as described in WO 2009/155471 at paragraph[0095] and [0096] except that the spectra are referenced to the chemicalshift of the solvent, tetrachloroethane-d₂; and/or(iii) a ratio of Mn(GPC)/Mn(¹H NMR) of 0.95 or less (preferably 0.90 orless, preferably 0.85 or less, preferably 0.80 or less). In the event ofconflict, g′ vis shall be used (if g′ vis cannot be determined, then theratio of percentage of saturated chain ends to percentage of allyl chainends shall be used; if the ratio of percentage of saturated chain endsto percentage of allyl chain ends cannot be determined, then the ratioof Mn(GPC)/Mn(¹H NMR) shall be used).

In embodiments where the branched polyolefins have an Mn (measured byGPC) of greater than 60,000 g/mol, the branched polyolefin has a g′ visof less than 0.90 (preferably 0.85 or less, preferably 0.80 or less)and, optionally, a bromine number which, upon complete hydrogenation,decreases by at least 50% (preferably by at least 75%).

In embodiments where the branched polyolefins have an Mn (measured by ¹HNMR) of less than 7,500 g/mol (preferably from 100 to 7,500 g/mol),comprise one or more alpha olefins (preferably propylene and/orethylene, preferably propylene) and, optionally, a C₄ to C₄₀ alphaolefin (preferably a C₄ to C₂₀ alpha olefin, preferably a C₄ to C₁₂alpha olefin, preferably butene, pentene, hexene, heptene, octene,nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene,and isomers thereof), and have:

(i) a ratio of percentage of saturated chain ends (preferably isobutylchain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably1.6 to 1.8), wherein the percentage of saturated chain ends isdetermined using ¹³C NMR as described in WO 2009/155471 at paragraph[0095] and [0096] except that the spectra are referenced to the chemicalshift of the solvent, tetrachloroethane-d₂; and/or(ii) a ratio of Mn(GPC)/Mn(¹H NMR) of 0.95 or less (preferably 0.90 orless, preferably 0.85 or less, preferably 0.80 or less).In an alternate embodiment, the branched polyolefins having an Mn(measured by ¹H NMR) of less than 7,500 g/mol (preferably from 100 to7,500 g/mol) has a g′ vis of 0.90 or less (preferably 0.85 or less,preferably 0.80 or less).

In one embodiment, the branched polyolefins produced herein have an Mn(measured by ¹H NMR) of 7,500 to 60,000 g/mol, comprise one or morealpha olefins (preferably propylene and/or ethylene, preferablypropylene) and, optionally, a C₄ to C₄₀ alpha olefin (preferably a C₄ toC₂₀ alpha olefin, preferably a C₄ to C₁₂ alpha olefin, preferablybutene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene,cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof), andhave:

(i) 50% or greater allyl chain ends, relative to total unsaturated chainends (preferably 60% or more, preferably 70% or more, preferably 75% ormore, preferably 80% or more, preferably 90% or more, preferably 95% ormore);

(ii) a g′ vis of 0.90 or less (preferably 0.85 or less, preferably 0.80or less); and/or a ratio of percentage of saturated chain ends(preferably isobutyl chain ends) to percentage of allyl chain ends of1.2 to 2.0 (preferably 1.6 to 1.8), wherein the percentage of saturatedchain ends is determined using ¹³C NMR as described in WO 2009/155471 atparagraph [0095] and [0096] except that the spectra are referenced tothe chemical shift of the solvent, tetrachloroethane-d₂, and/or a ratioof Mn(GPC)/Mn(¹H NMR) of 0.95 or less (preferably 0.90 or less,preferably 0.85 or less, preferably 0.80 or less);(iii) optionally, a peak melting point (Tm) of greater than 60° C.(preferably greater than 100° C., preferably from 60 to 180° C.,preferably from 80 to 175° C.);(iv) optionally, a heat of fusion (Hf) of greater than 7 J/g (preferablygreater than 15 J/g, greater than 30 J/g, greater than 50 J/g, greaterthan 60 J/g, or greater than 80 J/g);(v) optionally, an allyl chain end to internal vinylidene ratio ofgreater than 5:1 (preferably greater than 10:1);(vi) optionally, an allyl chain end to vinylidene chain end ratio ofgreater than 10:1 (preferably greater than 15:1); and(vii) optionally, an allyl chain end to vinylene chain end ratio ofgreater than 1:1 (preferably greater than 2:1, greater than 5:1, orgreater than 10:1).

In another embodiment, the branched polyolefins produced herein have anMn (measured by GPC) of greater than 60,000 g/mol, comprise one or morealpha olefins (preferably propylene and/or ethylene, preferablypropylene) and optionally, a C₄ to C₄₀ alpha olefin (preferably a C₄ toC₂₀ alpha olefin, preferably a C₄ to C₁₂ alpha olefin, preferablybutene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene,cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof) andhave:

(i) 50% or greater allyl chain ends, relative to total unsaturated chainends (preferably 60% or more, preferably 70% or more, preferably 75% ormore, preferably 80% or more, preferably 90% or more, preferably 95% ormore);

(ii) a g′ vis of 0.90 or less (preferably 0.85 or less, preferably 0.80or less);

(iii) optionally, a bromine number which, upon complete hydrogenation,decreases by at least 50% (preferably at least 75%);

(iv) optionally, a Tm of greater than 60° C. (preferably greater than100° C., preferably from 60 to 180° C., preferably from 80 to 175° C.);and

(v) optionally, an Hf of greater than 7 J/g (preferably greater than 15J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, orgreater than 80 J/g).

In another embodiment, the branched polyolefins produced herein have anMn (measured by ¹H NMR) of less than 7,500 g/mol (preferably from 100 to7,500 g/mol), comprise one or more alpha olefins (preferably propyleneand/or ethylene, preferably propylene) and, optionally, a C₄ to C₄₀alpha olefin (preferably a C₄ to C₂₀ alpha olefin, preferably a C₄ toC₁₂ alpha olefin, preferably butene, pentene, hexene, heptene, octene,nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene,and isomers thereof) and have:

(i) 50% or greater allyl chain ends, relative to total number ofunsaturated chain ends (preferably 60% or more, preferably 70% or more,preferably 75% or more, preferably 80% or more, preferably 90% or more,preferably 95% or more);

(ii) a ratio of percentage of saturated chain ends (preferably isobutylchain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably1.6 to 1.8), wherein the percentage of saturated chain ends isdetermined using ¹³C NMR as described in WO 2009/155471 at paragraph[0095] and [0096] except that the spectra are referenced to the chemicalshift of the solvent, tetrachloroethane-d₂, and/or a ratio ofMn(GPC)/Mn(¹H NMR) of 0.95 or less (preferably 0.90 or less, preferably0.85 or less, preferably 0.80 or less);(iii) optionally, a Tm of greater than 60° C. (preferably greater than100° C., preferably from 60 to 180° C., preferably from 80 to 175° C.);(iv) optionally, an Hf of greater than 7 J/g (preferably greater than 15J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, orgreater than 80 J/g);(v) optionally, an allyl chain end to internal vinylidene ratio ofgreater than 5:1 (preferably greater than 10:1);(vi) optionally, an allyl chain end to vinylidene chain end ratio ofgreater than 10:1 (preferably greater than 15:1); and(vii) optionally, an allyl chain end to vinylene chain end ratio ofgreater than 1:1 (preferably greater than 2:1, greater than 5:1, orgreater than 10:1).

In some embodiments, the branched polyolefins have a branching index, g′vis (as determined by GPC), of 0.90 or less (preferably 0.85 or less,preferably 0.80 or less), relative to a linear polymer of the samecomposition and microstructure.

The preferred branched polyolefins described herein have an Mn (measuredby ¹H NMR) of 7,500 to 60,000 g/mol or alternately greater than 60,000g/mol or alternately from 100 g/mol to less than 7,500 g/mol. Further, adesirable molecular weight range can be any combination of any uppermolecular weight limit with any lower molecular weight limit describedabove. Mn (¹H NMR) is determined according to the NMR method describedbelow in the Examples section. Mn may also be determined using a GPC-DRImethod, as described below. For the purpose of the claims, unlessindicated otherwise, Mn is determined by ¹H NMR.

In another embodiment, the branched polyolefins described herein have anMw (measured using a GPC-DRI method, as described below) of 1000 g/molor more (preferably from about 1,000 to about 400,000 g/mol, preferablyfrom about 2000 to 300,000 g/mol, preferably from about 3,000 to 200,000g/mol) and/or an Mz in the range of from about 1700 to about 150,000g/mol or preferably from about 800 to 100,000 g/mol, and/or an Mw/Mn inthe range of from about 1.2 to 20 (alternately from about 1.7 to 10,alternately from about 1.8 to 5.5).

In particular embodiments, the branched polyolefins described hereinhave a ratio of Mn(GPC)/Mn(¹H NMR) of 0.95 or less (preferably 0.90 orless, preferably 0.85 or less, preferably 0.80 or less). With respect toFIG. 1, FIG. 1 shows a plot of Mn as determined by GPC versus Mncalculated from ¹H NMR data, as shown below. The plot of the best fitline for the experimental data (shown as a solid line) lies below theparity plot (dashed line). The slope of the best fit line is 0.73065.

Mn is calculated from ¹H NMR data, assuming one unsaturation perpolyolefin chain. ¹H NMR data is collected at either room temperature or120° C. (for purposes of the claims, 120° C. shall be used) in a 5 mmprobe using a Varian spectrometer with a proton frequency of 250 MHz,400 MHz, or 500 MHz (for the purpose of the claims, a proton frequencyof 400 mHz is used). Data is recorded using a maximum pulse width of 45°C., 8 seconds between pulses and signal averaging 120 transients.Spectral signals are integrated and the number of unsaturation types per1000 carbons is calculated by multiplying the different unsaturationgroups by 1000 and dividing the result by the total number of carbons.Mn (¹H NMR) is calculated by dividing the total number of unsaturatedspecies into 14,000, and has units of g/mol.

Mn, Mw, Mz, carbon number, and g′ vis are measured by a GPC-DRI (GelPermeation Chromatograph-Differential Refractive Index) method using aHigh Temperature Size Exclusion Chromatograph (SEC, either from WatersCorporation or Polymer Laboratories), equipped with a DRI. Experimentaldetails, are described in: T. Sun, P. Brant, R. R. Chance, and W. W.Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001)and references therein. Three Polymer Laboratories PLgel 10 mm Mixed-Bcolumns are used. The nominal flow rate is 0.5 cm³/min, and the nominalinjection volume is 300 μl. The various transfer lines, columns anddifferential refractometer (the DRI detector) are contained in an ovenmaintained at 135° C. Solvent for the SEC experiment is prepared bydissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCBmixture is then filtered through a 0.7 μm glass pre-filter andsubsequently through a 0.1 μm Teflon filter. The TCB is then degassedwith an online degasser before entering the SEC. Polymer solutions areprepared by placing dry polymer in a glass container, adding the desiredamount of TCB, then heating the mixture at 160° C. with continuousagitation for about 2 hours. All quantities are measuredgravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/mL at room temperatureand 1.324 g/mL at 135° C. The injection concentration is from 1.0 to 2.0mg/mL, with lower concentrations being used for higher molecular weightsamples. Prior to running each sample the DRI detector and the injectorare purged. Flow rate in the apparatus is then increased to 0.5mL/minute, and the DRI is allowed to stabilize for 8 to 9 hours beforeinjecting the first sample. The concentration, c, at each point in thechromatogram is calculated from the baseline-subtracted DRI signal,I_(DRI), using the following equation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymersand 0.1 otherwise. Units of parameters used throughout this descriptionof the SEC method are: concentration is expressed in g/cm³, molecularweight is expressed in g/mol, and intrinsic viscosity is expressed indL/g.

The LS detector is a Wyatt Technology High Temperature mini-DAWN. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient [for purposes of thisinvention, A₂=0.0006 for propylene polymers, 0.0015 for butene polymersand 0.001 otherwise], (dn/dc)=0.104 for propylene polymers, 0.098 forbutene polymers and 0.1 otherwise, P(θ) is the form factor for amonodisperse random coil, and K_(o) is the optical constant for thesystem:

$K_{o} = \frac{4\pi^{2}{n^{2}( {d\;{n/d}\; c} )}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=690 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:η_(S) =c[η]+0.3(c[η])²where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum\;{c_{i}\lbrack\eta\rbrack}_{i}}{\sum\; c_{i}}$where the summations are over the chromatographic slices, i, between theintegration limits. The branching index g′ vis is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{k\; M_{v}^{\alpha}}$where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(v) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis. See Macromolecules, 2001,34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181-7183, forguidance on selecting a linear standard having similar molecular weightand comonomer content, and determining k coefficients and α exponents.

In some embodiments, the branched polyolefin has 50% or greater allylchain ends (preferably 60% or more, preferably 70% or more, preferably80% or more, preferably 90% or more, preferably 95% or more). Branchedpolyolefins generally have a chain end (or terminus) which is saturatedand/or an unsaturated chain end. The unsaturated chain end of theinventive polymers comprises “allyl chain ends.” An allyl chain end isrepresented by the formula:

where M represents the polymer chain. “Allylic vinyl group,” “allylchain end,” “vinyl chain end,” “vinyl termination,” “allylic vinylgroup” and “vinyl terminated” are used interchangeably in the followingdescription.

The “allyl chain end to vinylidene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylidene chain ends. In some embodiments, the allyl chain end tovinylidene chain end ratio is more than 10:1 (preferably greater than15:1).

The “allyl chain end to vinylene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylene chain ends. In some embodiments, the allyl chain end tovinylene chain end ratio is greater than 1:1 (preferably greater than2:1, greater than 5:1, or greater than 10:1).

The “allyl chain end to internal vinylidene ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofinternal (or non-terminal) vinylidene groups. In some embodiments, theallyl chain end to internal vinylidene ratio is greater than 5:1(preferably greater than 10:1).

The number of allyl chain ends, vinylidene chain ends and vinylene chainends is determined using ¹H NMR at 120° C. using deuteratedtetrachloroethane as the solvent on an at least 250 MHz NMRspectrometer, and in selected cases, confirmed by ¹³C NMR. Resconi hasreported proton and carbon assignments (neat perdeuteratedtetrachloroethane used for proton spectra, while a 50:50 mixture ofnormal and perdeuterated tetrachloroethane was used for carbon spectra;all spectra were recorded at 100° C. on a Bruker spectrometer operatingat 500 MHz for proton and 125 MHz for carbon) for vinyl terminatedpropylene oligomers in J. American Chemical Soc., 114, 1992, pp.1025-1032 that are useful herein. Allyl chain ends are reported as amolar percentage of the total number of moles of unsaturated groups(that is, the sum of allyl chain ends, vinylidene chain ends, vinylenechain ends, and the like).

The unsaturated chain ends may be further characterized by using bromineelectrometric titration, as described in ASTM D 1159. The bromine numberobtained is useful as a measure of the unsaturation present in thesample. In embodiments herein, branched polyolefins have a brominenumber which, upon complete hydrogenation, decreases by at least 50%(preferably by at least 75%).

The branched polyolefin also has at least one saturated chain end,preferably at least two saturated chain ends, per branched polyolefinmolecule. In some embodiments, the branched polyolefins produced hereinhave a ratio of percentage of saturated chain ends (preferably isobutylchain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably1.6 to 1.8), wherein the percentage of saturated chain ends isdetermined using ¹³C NMR as described in WO 2009/155471 at paragraph[0095] and [0096] except that the spectra are referenced to the chemicalshift of the solvent, tetrachloroethane-d₂. Where the branchedpolyolefins comprise propylene-derived units, the saturated chain endwhich may comprise an isobutyl chain end. An “isobutyl chain end” isdefined to be an end or terminus of a polymer, represented as shown inthe formula below:

where M represents the polymer chain. The structure of the branchedpolyolefin near the saturated chain end may differ, depending on thetypes and amounts of monomer(s) used, and method of insertion during thepolymerization process. In some preferred embodiments, where thebranched polyolefins comprise propylene-derived units and C₄ to C₄₀alpha olefin derived units, the structure of the polymer within fourcarbons of the isobutyl chain end is represented by one of the followingformulae:

where M represents the rest of the polymer chain and C_(m) representsthe polymerized monomer, each C_(m) may be the same or different, andwhere m is an integer from 2 to 8.

The percentage of isobutyl chain ends is determined using ¹³C NMR (asdescribed in the Example section) and the chemical shift assignments inResconi et al, J. Am. Chem. Soc. 114, 1992, pp. 1025-1032 for 100%propylene oligomers and reported herein for branched polyolefins.

In some embodiments, the branched polyolefin has a ratio of percentageof saturated chain ends (preferably isobutyl chain ends) to percentageof allyl chain ends of 1.2 to 2.0 (preferably 1.6 to 1.8), wherein thepercentage of saturated chain ends is determined using ¹³C NMR asdescribed in WO 2009/155471 at paragraph [0095] and [0096] except thatthe spectra are referenced to the chemical shift of the solvent,tetrachloroethane-d₂.

In other embodiments, the branched polyolefins described herein have aTm of greater than 60° C. (preferably greater than 100° C., preferablyfrom 60 to 180° C., preferably from 80 to 175° C.).

In other embodiments, the branched polyolefins described herein have anHf of greater than 7 J/g (preferably greater than 15 J/g, greater than30 J/g, greater than 50 J/g, greater than 60 J/g, or greater than 80J/g).

In other embodiments, the branched polyolefins described herein have aglass transition temperature (Tg) of less than 0° C. or less (asdetermined by differential scanning calorimetry as described below),preferably −10° C. or less, more preferably −20° C. or less, morepreferably −30° C. or less, more preferably −50° C. or less.

Tm, Hf, and Tg are measured using Differential Scanning calorimetry(DSC) using commercially available equipment such as a TA InstrumentsModel Q100. Typically, 6 to 10 mg of the sample, that has been stored atroom temperature for at least 48 hours, is sealed in an aluminum pan andloaded into the instrument at room temperature. The sample isequilibrated at 25° C., then it is cooled at a cooling rate of 10°C./min to −80° C. The sample is held at −80° C. for 5 min and thenheated at a heating rate of 10° C./min to 25° C. The glass transitiontemperature is measured from the heating cycle. Alternatively, thesample is equilibrated at 25° C. for 5 minutes, then heated at a heatingrate of 10° C./min to 200° C., followed by an equilibration at 200° C.for 5 minutes, and cooled at 10° C./min to −80° C. The endothermicmelting transition, if present, is analyzed for onset of transition andpeak temperature. The melting temperatures reported are the peak meltingtemperatures from the first heat unless otherwise specified. For samplesdisplaying multiple peaks, the melting point (or melting temperature) isdefined to be the peak melting temperature associated with the largestendothermic calorimetric response in that range of temperatures from theDSC melting trace. Areas under the DSC curve are used to determine theheat of transition (heat of fusion, Hf, upon melting or heat ofcrystallization, Hc, upon crystallization, if the Hf value from themelting is different from the Hc value obtained for the heat ofcrystallization, then the value from the melting (Tm) shall be used),which can be used to calculate the degree of crystallinity (also calledthe percent crystallinity). The percent crystallinity (X %) iscalculated using the formula: [area under the curve (in J/g)/H°(inJ/g)]*100, where H° is the heat of fusion for the homopolymer of themajor monomer component. These values for H° are to be obtained from thePolymer Handbook, Fourth Edition, published by John Wiley and Sons, NewYork 1999, except that a value of 290 J/g is used as the equilibriumheat of fusion)(H°) for 100% crystalline polyethylene, a value of 140J/g is used as the equilibrium heat of fusion)(H°) for 100% crystallinepolybutene, and a value of 207 J/g)(H°) is used as the heat of fusionfor a 100% crystalline polypropylene.

In another embodiment, any of the branched polyolefins described hereinhave a viscosity at 190° C. of greater than 50 mPa·sec, greater than 100mPa·sec, or greater than 500 mPa·sec. In other embodiments, the branchedpolyolefins have a viscosity of less than 15,000 mPa·sec, or less than10,000 mPa·sec. Viscosity is defined herein as resistance to flow and ismeasured at an elevated temperature using a Brookfield Viscometeraccording to ASTM D-3236.

In a preferred embodiment, any of the branched polyolefins describedherein comprises less than 3 wt % of functional groups selected fromhydroxide, aryls and substituted aryls, halogens, alkoxys, carboxylates,esters, acrylates, oxygen, nitrogen, and carboxyl (preferably less than2 wt %, less than 1 wt %, less than 0.5 wt %, less than 0.1 wt %, or 0wt %), based upon the weight of the copolymer.

In another embodiment, any of the branched polyolefins described hereincomprises at least 50 wt % (preferably at least 75 wt %, preferably atleast 90 wt %), based upon the weight of the copolymer composition, ofolefins having at least 36 carbon atoms (preferably at least 51 carbonatoms or at least 102 carbon atoms) as measured by ¹H NMR, assuming oneunsaturation per chain.

In another embodiment, the branched polyolefins comprise less than 20 wt% dimer and trimer (preferably less than 10 wt %, preferably less than 5wt %, more preferably less than 2 wt %, based upon the weight of thecopolymer composition), as measured by gas chromatography. “Dimer” (and“trimer”) are defined as copolymers having two (or three) monomer units,where the monomer units may be the same or different from each other(where “different” means differing by at least one carbon). Products areanalyzed by gas chromatograph (Agilent 6890N with auto-injector) usinghelium as a carrier gas at 38 cm/sec. A column having a length of 60 m(J & W Scientific DB-1, 60 m×0.25 mm I.D.×1.0 μm film thickness) packedwith a flame ionization detector (FID), an Injector temperature of 250°C., and a Detector temperature of 250° C. are used. The sample isinjected into the column in an oven at 70° C., then heated to 275° C.over 22 minutes (ramp rate 10° C./min to 100° C., 30° C./min to 275° C.,hold). An internal standard, usually the monomer, is used to derive theamount of dimer or trimer product that is obtained. Yields of dimer andtrimer product are calculated from the data recorded on thespectrometer. The amount of dimer or trimer product is calculated fromthe area under the relevant peak on the GC trace, relative to theinternal standard.

In another embodiment, any of the branched polyolefins described hereincontain less than 25 ppm hafnium or zirconium, preferably less than 10ppm hafnium or zirconium, preferably less than 5 ppm hafnium orzirconium, based on the yield of polymer produced and the mass ofcatalyst employed. ICPES (Inductively Coupled Plasma EmissionSpectrometry), which is described in J. W. Olesik, “Inductively CoupledPlasma-Optical Emission Spectroscopy,” in the Encyclopedia of MaterialsCharacterization, C. R. Brundle, C. A. Evans, Jr. and S. Wilson, eds.,Butterworth-Heinemann, Boston, Mass., 1992, pp. 633-644, is used todetermine the amount of an element in a material.

In yet other embodiments, the branched polyolefin is a liquid at 25° C.

In some embodiments, the branched polyolefin may be a homopolymer ofpropylene. The branched polyolefin may also be a copolymer, aterpolymer, or so on. In some embodiments herein, the branchedpolyolefin comprises from about 0.1 to 99.9 mol % (preferably from about5 to about 90 mol %, from about 15 to about 85 mol %, from about 25 toabout 80 mol %, from about 35 to about 75 mol %, or from about 45 toabout 95 mol %) of propylene. In other embodiments, the branchedpolyolefin comprises greater than 5 mol % (preferably greater than 10mol %, greater than 20 mol %, greater than 35 mol %, greater than 45 mol%, greater than 55 mol %, greater than 70 mol %, or greater than 85 mol%) of propylene.

In some embodiments, the branched polyolefin comprises C₄ to C₄₀monomers, preferably C₄ to C₂₀ monomers, or preferably C₄ to C₁₂monomers. The C₄ to C₄₀ monomers, may be linear or cyclic. The cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include hetero atoms and/or one or more functional groups.Exemplary monomers include butene, pentene, hexene, heptene, octene,nonene, decene, undecene, dodecene, norbornene, cyclopentene,cycloheptene, cyclooctene, cyclododecene, 7-oxanorbornene, substitutedderivatives thereof, and isomers thereof, preferably hexane, heptene,octene, nonene, decene, dodecene, cyclooctene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, cyclopentene, norbornene, and their respectivehomologs and derivatives.

In some embodiments, the branched polyolefin comprises two or moredifferent C₄ to C₄₀ monomers, three or more different C₄ to C₄₀monomers, or four or more different C₄ to C₄₀ monomers. In someembodiments herein, the branched polyolefin comprises from about 0.1 to99.9 mol % (preferably from about 5 to about 90 mol %, from about 15 toabout 85 mol %, from about 25 to about 80 mol %, from about 35 to about75 mol %, or from about 45 to about 95 mol %) of at least one(preferably two or more, three or more, four or more, and the like) C₄to C₄₀ (preferably butene, pentene, hexene, heptene, octene, nonene,decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, andisomers thereof) monomers. In other embodiments, the branched polyolefincomprises greater than 5 mol % (preferably greater than 10 mol %,greater than 20 mol %, greater than 35 mol %, greater than 45 mol %,greater than 55 mol %, greater than 70 mol %, or greater than 85 mol %)of C₄ to C₄₀ (preferably butene, pentene, hexene, octene, and decene)monomer.

In some embodiments, the branched polyolefins are homopolypropylene,propylene/ethylene copolymers, propylene/hexene copolymers,propylene/octene copolymers, propylene/decene copolymers,propylene/hexene/octene terpolymers, propylene/hexene/deceneterpolymers, propylene/octene/decene terpolymers, and the like.

Uses of Vinyl Terminated Polymers

The vinyl terminated branched polymers prepared herein may befunctionalized by reacting a heteroatom containing group with the allylgroup of the polymer, with or without a catalyst. Examples includecatalytic hydrosilylation, hydroformylation, hydroboration, epoxidation,hydration, dihydroxylation, hydroamination, or maleation with or withoutactivators such as free radical generators (e.g., peroxides).

In some embodiments, the vinyl terminated branched polymers producedherein are functionalized as described in U.S. Pat. No. 6,022,929; A.Toyota, T. Tsutsui, and N. Kashiwa, Polymer Bulletin 48, pp. 213-219,2002; J. Am. Chem. Soc., 1990, 112, pp. 7433-7434; and U.S. Ser. No.12/487,739 filed on Jun. 19, 2009 (Published as WO 2009/155472).

The functionalized branched polymers can be used in oil additivation andmany other applications. Preferred uses include additives for lubricantsand/or fuels. Preferred heteroatom containing groups include amines,aldehydes, alcohols, acids, succinic acid, maleic acid, and maleicanhydride.

In particular embodiments herein, the vinyl terminated branched polymersdisclosed herein, or functionalized analogs thereof, are useful asadditives. In some embodiments, the vinyl terminated polymers disclosedherein, or functionalized analogs thereof, are useful as additives to alubricant. Particular embodiments relate to a lubricant comprising thevinyl terminated polymers disclosed herein, or functionalized analogsthereof.

In other embodiments, the vinyl terminated branched polymers disclosedherein may be used as monomers for the preparation of polymer products.Processes that may be used for the preparation of these polymer productsinclude coordinative polymerization and acid-catalyzed polymerization.In some embodiments, the polymeric products may be homopolymers. Forexample, if a vinyl terminated polymer (A) were used as a monomer, it ispossible to form a homopolymer product with the formulation (A)_(n),where n is the degree of polymerization.

In other embodiments, the polymer products formed from mixtures ofmonomer vinyl terminated polymers may be mixed polymers, comprising twoor more repeating units that are different from each. For example, if avinyl terminated polymer (A) and a different vinyl terminated polymer(B) were copolymerized, it is possible to form a mixed polymer productwith the formulation (A)_(n)(B)_(m), where n is the number of molarequivalents of vinyl terminated polymer (A) and m is the number of molarequivalents of vinyl terminated polymer (B) that are present in themixed polymer product.

In yet other embodiments, polymer products may be formed from mixturesof the vinyl terminated branched polymer with another alkene. Forexample, if a vinyl terminated branched polymer (A) and alkene (B) werecopolymerized, it is possible to form a mixed polymer product with theformulation (A)_(n)(B)_(m), where n is the number of molar equivalentsof vinyl terminated polymer and m is the number of molar equivalents ofalkene that are present in the mixed polymer product.

In another embodiment, this invention relates to a functionalizedbranched polyolefin comprising the reaction product of a heteroatomcontaining group and any vinyl terminated branched polyolefin describedherein, preferably where the functional group comprises one or moreheteroatoms selected from the group consisting of P, O, S, N, Br, Cl, F,I, and/or B, and the functionalized branched polyolefin has 0.60 to 1.2,alternately, 0.75 to 1.10, functional groups per chain (preferablyassuming that Mn has not altered by more than 15% as compared to the Mnof the vinyl terminated branched polyolefin prior to functionalizationand optional derivatization). The number of functional groups per chain(F/Mn) is determined by ¹H NMR as described in WO 2009/155472 (See pages26 to 27, paragraphs [00111] to [00114], including that VDRA is VRDA,which is the normalized integrated signal intensity for the vinylideneresonances between from about 4.65 to 4.85 ppm and the vinyleneresonances at from about 5.15 to 5.6 ppm.)

Preferred heteroatom containing groups comprise one or more ofsulfonates, amines, aldehydes, alcohols, or acids, preferably theheteroatom containing group comprises an epoxide, succinic acid, maleicacid or maleic anhydride, alternately the heteroatom containing groupcomprises one or more of acids, esters, anhydrides, acid-esters,oxycarbonyls, carbonyls, formyls, formylcarbonyls, hydroxyls, and acetylhalides.

Percent functionalization of the branched polyolefin=(F*100)/(F+VI+VE).The number of vinyl groups/1000 carbons (VI*) and number of vinylidenegroups/1000 carbons (VE*) for the functionalized branched polyolefin aredetermined from the ¹H NMR spectra of the functionalized polyolefin inthe same manner as VI and VE for the unfunctionalized polymer.Preferably, the percent functionalization of the branched polyolefin is75% or more, preferably 80% or more, preferably 90% or more, preferably95% or more.

In another embodiment the functionalized polyolefins described hereinhave the same Mn, and/or Mw and/or Mz as, or up to 15% greater than(preferably up to 10% greater than), as the starting vinyl terminatedpolyolefins, “same” is defined to mean within 5%.

In another embodiment, the vinyl terminated branched polyolefinsdescribed herein can be use in any process, blend, product, orcomposition disclosed in WO 2009/155472, which is incorporated byreference herein. In some embodiments, the composition is a lubricantblend, an adhesive, or a wax. In some embodiments, the invention relatesto the use of the composition as a lubricant blend, an adhesive, or awax.

In another embodiment this invention relates to:

1. A process for polymerization, comprising:

(i) contacting, preferably at a temperature greater than 35° C. (morepreferably in the range of from about 35 to 150° C., from 40 to 140° C.,from 60 to 140° C., or from 80 to 130° C.) and, optionally, at apressure in the range of from about 0.35 to 10 MPa (preferably from 0.45to 6 MPa or from 0.5 to 4 MPa), one or more monomers comprising ethyleneand/or propylene (preferably propylene) and optionally, one or more C₄to C₄₀ alpha olefin monomers (preferably C₄ to C₂₀ alpha olefinmonomers, preferably C₄ to C₁₂ alpha olefin monomers, preferably butene,pentene, hexene, heptene, octene, nonene, decene, cyclopentene,cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof), with acatalyst system capable of producing a branched polyolefin, preferablythe catalyst system comprises a metallocene catalyst compound and anactivator (preferably the activator is a non-alumoxane compound,preferably alumoxane is present at 0 wt %, preferably the activator is anon-coordinating anion activator) (alternately the catalyst system is amixed catalyst system comprising one or more non-metallocene catalystcompounds, one or more metallocene catalyst compounds, or a combinationthereof, preferably the catalyst system comprises a single metallocenecatalyst), wherein the metallocene catalyst compound is represented bythe following formula:

whereM is selected from the group consisting of zirconium or hafnium(preferably hafnium);each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines,ethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system) (preferably X is a halide or a hydrocarbylradical having from 1 to 20 carbon atoms, preferably X is chloride ormethyl);each R¹, R², R³, R⁴, R⁵, and R⁶, is, independently, hydrogen or asubstituted or unsubstituted hydrocarbyl group, a heteroatom orheteroatom containing group;further provided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated; andfurther provided that any of adjacent R⁴, R⁵, and R⁶ groups may form afused ring or multicenter fused ring system where the rings may bearomatic, partially saturated or saturated;T is a bridging group represented by the formula R₂ ^(a)J, where J isone or more of C, Si, Ge, N or P (preferably J is Si), and each R^(a)is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl or a C₁ toC₂₀ substituted hydrocarbyl, (preferably R^(a) is methyl, ethyl,chloride) provided that at least one R³, preferably both, are asubstituted or unsubstituted phenyl group, if any of R¹, R², R⁴, R⁵ orR⁶ are not hydrogen;(ii) preferably converting at least 50 mol % of the monomer topolyolefin, more preferably at least 60 mol %, at least 70 mol %, atleast 80 mol %; and(iii) obtaining a branched polyolefin having greater than 50% allylchain ends, relative to total unsaturated chain ends (preferably 60% ormore, preferably 70% or more, preferably 80% or more, preferably 90% ormore, preferably 95% or more) and a Tm of 60° C. or more (preferably100° C. or more, preferably 120° C. or more).2. The processes of paragraph 1 or 12, wherein butene comonomer ispresent and a mixed butene stream is the source of the butene comonomer.3. The processes of paragraphs 1, 2, or 12, wherein the activator is abulky activator represented by the formula:

whereeach R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ canform one or more saturated or unsaturated, substituted or unsubstitutedrings (preferably R₂ and R₃ form a perfluorinated phenyl ring);L is an neutral Lewis base;(L-H)⁺ is a Bronsted acid;d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.4. The process of paragraph 3, wherein the bulky activator is at leastone of: trimethylammonium tetrakis(perfluoronaphthyl)borate,triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, and[4-t-butyl-PhNMe₂H][(m-C₆F₅—C₆F₄)₄B].5. The process of paragraph 1, 2, 3, 4, or 12, wherein the processoccurs in a single reaction zone (preferably a solution polymerization).6. The process of paragraph 1, 2, 3, 4, 5, or 12, wherein theproductivity is 4500 g/mmol or more (preferably 5000 g/mmol or more,preferably 10,000 g/mmol or more, preferably 50,000 g/mmol or more;alternately the productivity is at least 80,000 g/mmol, preferably atleast 150,000 g/mmol, preferably at least 200,000 g/mmol, preferably atleast 250,000 g/mmol, preferably at least 300,000 g/mmol).7. The process of paragraph 1, 2, 3, 4, 5, 6, or 12, wherein theresidence time of the polymerization is up to 300 minutes (preferably inthe range of from about 1 to 300 minutes, preferably from about 5 to 250minutes, or preferably from about 10 to 120 minutes).8. A branched polyolefin produced by the process of paragraphs 1 to 7 or12, having an Mn (measured by ¹H NMR) of 7,500 to 60,000 g/mol,comprising one or more alpha olefins (preferably propylene and/orethylene, preferably propylene) and, optionally, one or more C₄ to C₄₀alpha olefin monomers (preferably C₄ to C₂₀ alpha olefin monomers,preferably C₄ to C₁₂ alpha olefin monomers, preferably butene, pentene,hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene,cyclooctene, cyclooctadiene, and isomers thereof) and having:(i) 50% or greater allyl chain ends, relative to total number ofunsaturated chain ends (preferably 60% or more, preferably 70% or more,preferably 75% or more, preferably 80% or more, preferably 90% or more,preferably 95% or more);(ii) a g′ vis of 0.90 or less (preferably 0.85 or less, preferably 0.80or less) and/or a ratio of percentage of saturated chain ends(preferably isobutyl chain ends) to percentage of allyl chain ends of1.2 to 2.0 (preferably 1.6 to 1.8), and/or a ratio of Mn(GPC)/Mn(¹H NMR)of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less,preferably 0.80 or less);(iii) optionally, a Tm of greater than 60° C. (preferably greater than100° C., preferably from 60 to 180° C., preferably from 80 to 175° C.);(iv) optionally, an Hf of greater than 7 J/g (preferably greater than 15J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, orgreater than 80 J/g);(v) optionally, an allyl chain end to internal vinylidene ratio ofgreater than 5:1 (preferably greater than 10:1);(vi) optionally, an allyl chain end to vinylidene chain end ratio ofgreater than 10:1 (preferably greater than 15:1); and(vii) optionally, an allyl chain end to vinylene chain end ratio ofgreater than 1:1 (preferably greater than 2:1, greater than 5:1, orgreater than 10:1).9. A branched polyolefin produced by the process of paragraphs 1 to 7 or12, having an Mn (measured by GPC) of greater than 60,000 g/mol,comprising one or more alpha olefins (preferably propylene and/orethylene, preferably propylene) and, optionally, one or more C₄ to C₄₀alpha olefin monomers (preferably C₄ to C₂₀ alpha olefin monomers,preferably C₄ to C₁₂ alpha olefin monomers, preferably butene, pentene,hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene,cyclooctene, cyclooctadiene, and isomers thereof) and having:(i) 50% or greater allyl chain ends, relative to total number ofunsaturated chain ends (preferably 60% or more, preferably 70% or more,preferably 75% or more, preferably 80% or more, preferably 90% or more,preferably 95% or more);(ii) having a g′ vis of 0.90 or less (preferably 0.85 or less,preferably 0.80 or less);(iii) optionally, a bromine number which, upon complete hydrogenation,decreases by at least 50% (preferably at least 75%);(iv) optionally, a Tm of greater than 60° C. (preferably greater than100° C., preferably from 60 to 180° C., preferably from 80 to 175° C.);and(v) optionally, an Hf of greater than 7 J/g (preferably greater than 15J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, orgreater than 80 J/g).10. A branched polyolefin produced by the process of paragraph 1 to 7 or12, having an Mn (measured by ¹H NMR) of less than 7,500 g/mol,preferably from 100 up to 7,500 g/mol, comprising one or more alphaolefins (preferably propylene and/or ethylene, preferably propylene)and, optionally, one or more C₄ to C₄₀ alpha olefin monomers (preferablyC₄ to C₂₀ alpha olefin monomers, preferably C₄ to C₁₂ alpha olefinmonomers, preferably butene, pentene, hexene, heptene, octene, nonene,decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, andisomers thereof) and having:(i) 50% or greater allyl chain ends, relative to total number ofunsaturated chain ends (preferably 60% or more, preferably 70% or more,preferably 75% or more, preferably 80% or more, preferably 90% or more,preferably 95% or more);(ii) a ratio of percentage of saturated chain ends (preferably isobutylchain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably1.6 to 1.8), and/or a ratio of Mn(GPC)/Mn(¹H NMR) of 0.95 or less(preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 orless);(iii) optionally, a Tm of greater than 60° C. (preferably greater than100° C., preferably from 60 to 180° C., preferably from 80 to 175° C.);(iv) optionally, an Hf of greater than 7 J/g (preferably greater than 15J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, orgreater than 80 J/g);(v) optionally, an allyl chain end to internal vinylidene ratio ofgreater than 5:1 (preferably greater than 10:1);(vi) optionally, an allyl chain end to vinylidene chain end ratio ofgreater than 10:1 (preferably greater than 15:1); and(vii) optionally, an allyl chain end to vinylene chain end ratio ofgreater than 1:1 (preferably greater than 2:1, greater than 5:1, orgreater than 10:1).11. A functionalized branched polyolefin of paragraphs 8 to 10, whereinthe functional group is selected from amines, aldehydes, alcohols,acids, succinic acid, maleic acid, and maleic anhydride.12. A process for polymerization, comprising:(i) contacting, at a temperature greater than 35° C. (preferably in therange of from about 35 to 150° C., from 40 to 140° C., from 60 to 140°C., or from 80 to 130° C.) and, optionally, a pressure in the range offrom about 0.35 to 10 MPa (preferably from 0.45 to 6 MPa or from 0.5 to4 MPa), one or more monomers comprising ethylene and/or propylene(preferably propylene) and optionally, one or more C₄ to C₄₀ alphaolefin monomers (preferably C₄ to C₂₀ alpha olefin monomers, preferablyC₄ to C₁₂ alpha olefin monomers, preferably butene, pentene, hexene,heptene, octene, nonene, decene, cyclopentene, cycloheptene,cyclooctene, cyclooctadiene, and isomers thereof), with a catalystsystem capable of producing a branched polyolefin, preferably thecatalyst system comprises a metallocene catalyst compound and anactivator (preferably the activator is a non-alumoxane compound,preferably alumoxane is present at 0 wt %, preferably the activator is anon-coordinating anion activator) (alternately the catalyst system is amixed catalyst system comprising one or more non-metallocene catalystcompounds, one or more metallocene catalyst compounds, or a combinationthereof, preferably the catalyst system comprises a single metallocenecatalyst), wherein the metallocene catalyst compound is represented bythe following formula:

whereM is selected from the group consisting of zirconium or hafnium(preferably hafnium);each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines,ethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system) (preferably X is a halide or a hydrocarbylradical having from 1 to 20 carbon atoms, preferably X is chloride ormethyl);each R¹, R², R³, R⁴, R⁵, and R⁶, is, independently, hydrogen or asubstituted or unsubstituted hydrocarbyl group, a heteroatom orheteroatom containing group;further provided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated; andfurther provided that any of adjacent R⁴, R⁵, and R⁶ groups may form afused ring or multicenter fused ring system where the rings may bearomatic, partially saturated or saturated;T is a bridging group represented by the formula R₂ ^(a)J, where J isone or more of C, Si, Ge, N or P (preferably J is Si), and each R^(a)is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl or a C₁ toC₂₀ substituted hydrocarbyl, (preferably R^(a) is methyl, ethyl,chloride) provided that at least one R³, preferably both, are asubstituted or unsubstituted phenyl group, if any of R¹, R², R⁴, R⁵ orR⁶ are not hydrogen;(ii) converting at least 50 mol % of the monomer to polyolefin(preferably at least 60 mol %, at least 70 mol %, at least 80 mol %);and(iii) obtaining a branched polyolefin having greater than 50% allylchain ends, relative to total unsaturated chain ends (preferably 60% ormore, preferably 70% or more, preferably 80% or more, preferably 90% ormore, preferably 95% or more) and a Tm of 60° C. or more (preferably100° C. or more, preferably 120° C. or more).

EXAMPLES Product Characterization

Products were characterized by ¹H NMR, GPC-3D, and DSC, as indicatedabove.

Metallocenes Used in Examples

The following metallocenes were used in the examples below.

Metallocene Structure A

B

C

Metallocenes A and C were obtained from Albemarle (Baton Rouge, La.) andused without further purification. Metallocene B was synthesized asshown below.Synthesis of Metallocene B

Typical dry-box procedures for synthesis of air-sensitive compounds werefollowed including using dried glassware (90° C., 4 hours) and anhydroussolvents purchased from Sigma Aldrich (St. Louis, Mo.) which werefurther dried over 3 A sieves. All reagents were purchased fromSigma-Aldrich (Milwaukee, Wis.) and used without further purification,unless otherwise noted.

The dichloride precursor of Metallocene B (B—Cl₂) was obtained fromAlbemarle, and converted to Metallocene B using the following procedure:Under inert atmosphere, in a purged Vacuum Atmospheres™ dry box, 3.02 gof B—Cl₂ was dissolved in 150 mL of dried toluene in a 250 mL singleneck round-bottom flask. To this 4.0 mL (5 eq) of 3.0M methylmagnesiumbromide was added dropwise. The solution was heated in an oil bath at90° C. overnight. The mixture was then allowed to cool to roomtemperature, at which time 10.0 mL of trimethylsilylchloride was addeddrop-wise. After stirring for 10 min, 10.0 mL of dried 1,4-dioxane wasadded and the mixture stirred an additional 10 min. The mixture was thenfiltered through an oven dried fine fritted funnel to remove magnesiumsalts. The flask was rinsed with about 20 mL n-pentane and this wascombined with the filtrate by passing through the frit. Solvent wasremoved under vacuum to yield 2.23 g of Metallocene B as an off-whitepowder (74% yield).

Activators Used in Examples

The following activators were used in the examples below. Activators Iand III were purchased from Albemarle. Activator II was purchased fromSingle Site Catalyst.

Activator Chemical Name IDimethylaniliniumtetrakis(pentafluorophenyl)borate IITrityl(perfluorophenyl)borate IIIDimethylaniliniumtetrakis(perfluoronaphthyl)boratePolymerization Conditions for Examples 1-2

All of the examples were produced in a 0.5-liter Autoclave reactoroperated in the continuous stirred-tank solution process. The autoclavewas equipped with a stirrer, a water-cooling/steam-heating element witha temperature controller, and a pressure controller. Solvents, monomerssuch as propylene were first purified by passing through a three-columnpurification system. Purification columns were regenerated periodicallywhenever there was evidence of lower activity of polymerization.

The solvent feed to the reactors was measured by a mass-flow meter. APulsa feed pump controlled the solvent flow rate and increased thesolvent pressure to the reactors. The compressed, liquefied propylenefeed was measured by a mass flow meter and the flow was controlled by aPulsa feed pump. The solvent and monomers were fed into a manifoldfirst. The mixture of solvent and monomers were then chilled to about−15° C. by passing through a chiller prior to feeding into the reactorthrough a single tube. The collected samples were first air-dried in ahood to evaporate most of the solvent, and then dried in a vacuum ovenat a temperature of about 90° C. for about 12 hours. The vacuum ovendried samples were weighed to obtain yields. Monomer conversion wascalculated basing the polymer yield on the amount of monomers fed intothe reactor. All the reactions were carried out at a pressure of about2.4 MPa/g.

Catalysts used in the following examples were rac-dimethylsilylbisindenyl hafnium dimethyl (Catalyst A), rac-dimethylsilybis(2-methylindenyl)zirconium dimethyl (Catalyst B), andrac-dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl(Catalyst C). The activators used were N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate (Activator I), trityltetrakis(pentafluorophenyl) borate (Activator II), and N,N-dimethylanilinium tetrakis(heptafluoro-2-naphthyl) borate (Activator III). Allof the metallocene catalysts were preactivated with an activator at amolar ratio of about 1:1 in 900 ml of toluene. All catalyst solutionswere kept in an inert atmosphere and fed into reactors by meteringpumps. Tri-n-octylaluminum (TNOAL) solution (available from SigmaAldrich, Milwaukee, Wis.) was further diluted in isohexane and used as ascavenger.

Propylene Polymerizations

The polymerization conditions, % conversion of feed, and catalystproductivity are listed in Table 1, below. In all runs, inlet propylenefeed concentration was between 3.5 and 4 M. Two standard cubiccentimeter of H₂ was used in the feed of Run #42. Tri(n-octyl)aluminum(TNOAL) was used throughout as scavenger. Molar ratio of TNOAL tometallocene was about 20. Residence time was constant at 5 minutes.

TABLE 1 Conversion and Productivity % RUN Met.¹ Act.² T_(p), ° C.Conversion* Productivity × 10³ kg/mol 1 B I 100 73.82 4.5 2 B I 90 77.004.7 3 B I 80 77.64 4.7 4 B I 70 77.82 4.7 5 B I 60 78.14 4.8 6 B II 6064.34 15.7 7 B II 70 65.23 15.9 8 B II 75 64.99 15.9 9 B II 80 67.2416.4 10 B II 85 66.39 16.2 11 B II 90 63.51 15.5 12 B II 95 61.03 14.913 B II 100 60.77 14.8 14 B II 105 53.86 13.1 15 B II 110 57.45 14.0 16B III 120 63.61 9.8 17 B III 110 66.43 10.2 18 B III 100 62.79 15.3 19 BIII 90 66.89 16.3 20 B III 80 68.39 16.7 21 B III 70 59.36 29.6 22 C I125 94.07 46.5 23 C I 120 95.68 47.3 24 C I 115 98.11 48.6 25 C I 11098.79 48.9 26 C I 105 100.61 46.9 27 C I 100 100.71 66.2 28 C I 95100.64 66.2 29 C I 90 100.39 66.0 30 C II 130 65.68 1.83 31 C II 12067.36 32.4 32 C II 110 70.14 33.3 33 C II 100 72.61 34.6 34 C II 9073.54 36.3 35 C II 80 73.57 36.3 36 C III 130 57.93 28.6 37 C III 12060.79 30.0 38 C III 110 62.04 30.6 39 C III 100 62.46 30.8 40 C III 9063.43 31.3 41 A I 90 — — 42 A I 80 — — 43 A I 130 73.90 5.4 44 A I 12081.80 6.0 45 A I 110 88.10 6.4 46 A I 100 85.60 6.3 47 A I 90 86.10 6.348 A I 80 89.40 6.5 49 A I 70 — — 50 A I 60 89.90 6.6 51 A II 130 62.574.6 52 A II 120 68.43 5.0 53 A II 110 71.86 5.3 54 A II 100 73.61 5.4 55A II 90 70.18 5.1 56 A II 80 69.71 5.1 57 A II 70 70.71 5.2 58 A II 60 —— 59 A III 130 77.25 5.7 60 A III 120 79.04 5.8 61 A III 110 81.46 6.062 A III 100 81.36 6.0 63 A III 90 77.11 5.7 64 A III 80 82.25 6.0 65 AIII 70 79.57 5.8 KEY: ¹Met. = metallocene, ²Act. = Activator; T_(p) =polymerization reaction temperature; *Propylene conversion calculated tobe >100% is taken to be 100%.

Propylene conversion was high: 53 to 100%. Productivity of Metallocene Cwas observed to be 3 to 6 times higher than that of Metallocene A. Theproductivity of Metallocene B was comparable to Metallocene C, in mostcases.

Characterization of Polymer Products

Differential Scanning Calorimetry (DSC)

Polymer from Runs 1-65 were analyzed using DSC. Data from the analysisof some of the polymer products is shown in the Table 2, below.

TABLE 2 Thermal Characterization of Polypropylene Products Polymer Met.¹Act.² T_(p), ° C. Tm, ° C. Hf, J/g 2 B I 90 — — 3 B I 80 80.29 28.08 4 BI 70 99.74 38.85 5 B I 60 117.76 59.14 6 B II 60 137.0 82.2 7 B II 70129.8 76.8 8 B II 75 122.4 39.9 9 B II 80 — — 10 B II 85 109.8 69.5 11 BII 90 107.8 52.4 12 B II 95 100.1 53.7 13 B II 100 97.47 42.8 14 B II105 98.1 59.29 15 B II 110 78.76 20.1 16 B III 120 65.6 10.09 17 B III110 80.6 32.1 18 B III 100 110.08 53.9 19 B III 90 106.99 64.1 20 B III80 113.68 80.7 21 B III 70 137.95 89.6 22 C I 125 131.93 82.65 23 C I120 134.32 87.26 24 C I 115 136.91 84.17 25 C I 110 140.77 90.01 26 C I105 142.31 92.33 27 C I 100 145.07 97.75 28 C I 95 146.07 96.40 29 C I90 148.15 103.70 30 C II 130 127.14 78.58 31 C II 120 132.64 84.16 32 CII 110 138.27 91.6 33 C II 100 140.83 127.15 34 C II 90 145.42 95.89 35C II 80 151.24 103.60 36 C III 130 132.33 89.6 37 C III 120 137.18 87.838 C III 110 143.44 96.72 39 C III 100 146.0 100.70 40 C III 90 152.8593.78 41 A I 90 — — 42 A I 80 86.6 31.0 43 A I 130 69.04 19.59 44 A I120 80.38 23.63 45 A I 110 90.25 35.64 46 A I 100 99.38 44.54 47 A I 90107.78 56.51 48 A I 80 118.01 61.19 49 A I 70 127.57 67.58 50 A I 60131.25 73.25 51 A II 130 57.8 10.10 52 A II 120 62.1 15.8 53 A II 11075.16 27.97 54 A II 100 89.6 38.24 55 A II 90 103.7 52.49 56 A II 80119.0 61.29 57 A II 70 127.0 70.86 58 A II 60 104.0 47.64 59 A III 13062.4 7.6 60 A III 120 79.4 24.78 61 A III 110 93.16 33.78 62 A III 100105.38 50.96 63 A III 90 116.76 60.97 64 A III 80 128.96 77.76 65 A III70 134.7 76.86 KEY: ¹Met. = metallocene, ²Act. = Activator; T_(p) ispolymerization reaction temperature; *Propylene conversion calculated tobe >100% is taken to be 100%.

Metallocene C offers excellent melting point capability. Increasingpolymerization temperature results in a decrease in melting point. Thedecrease in melting point is thought to arise from a higher populationof stereo- and region-defects in the products. Among the activators,Activator III appears to be the most effective at increasing the meltingpoint.

Gel Permeation Chromatography (GPC-3D)

GPC 3D results for some of the polymers are summarized in Table 3.

TABLE 3 Summary of GPC-3D Data Molecular Weight Moments Polym Temp ° C.Run No. Mn Mw Mz g′vis Metallocene B/Activator I 100 1 — — — — 90 23,590 5,450 7,900 80 3 5,440 8,330 12,630 0.91 70 4 8,810 13,040 18,8600.98 60 5 14,240 21,740 31,360 0.97 Metallocene B/Activator II 60 628,014 48,576 69,668 0.976 70 7 3,438 28,203 40,678 0.957 75 8 6,40615,960 25,601 0.961 80 9 1,646 8,222 12,873 0.972 85 10 3,391 11,71817,971 0.986 90 11 5,013 10,289 16,529 0.974 95 12 1,698 4,809 8,0410.954 100 13 2,439 7,490 11,719 0.970 105 14 2,266 6,726 13,140 0.943110 15 1,308 4,515 7,773 0.859 Metallocene B/Activator III 120 16 2,69310,701 23,039 0.977 110 17 8,427 19,411 35,295 0.887 100 18 5,751 33,93461,807 1.005 90 19 7,980 13,832 21,377 0.970 80 20 8,688 18,937 28,5330.942 70 21 26,036 45,472 70,218 1.008 Metallocene C/Activator I 125 226,324 16,922 30,721 — 120 23 6,692 20,476 37,823 0.832 115 24 9,82024,758 44,867 0.83 110 25 9,360 29,356 55,191 0.825 105 26 13,136 36,62469,815 0.801 100 27 18,665 47,461 87,325 — 95 28 19,736 57,000 109,4010.814 90 29 32,110 73,822 151,184 0.822 Metallocene C/Activator II 12031 6,810 17,887 35,399 0.832 110 32 9,029 26,094 49,403 0.801 100 3316,553 39,113 73,365 0.796 90 34 24,989 60,579 112,107 0.787 80 3540,160 94,821 175,322 0.812 Metallocene C/Activator III 130 36 8,67921,099 45,377 0.818 120 37 16,218 35,192 70,346 0.816 110 38 24,28659,994 119,250 0.791 100 39 36,835 96,306 183,656 0.807 90 40 56,615158,033 303,296 0.800 Metallocene A/Activator I 90 41 3,641 21,14136,168 0.876 80 42 8,921 21,925 34,197 0.966 130 43 3,117 7,247 60,5271.089 120 44 — — — — 110 45 6,131 12,490 21,444 0.946 100 46 — — — — 9047 15,592 27,769 45,011 0.925 80 48 — — — — 70 49 37,866 73,700 116,1210.952 60 50 — — — — Metallocene A/Activator II 130 51 156 7,320 39,8330.695 120 52 3,235 6,773 12,905 0.941 110 53 405 12,346 40,531 0.844 10054 7,632 15,444 26,660 0.915 90 55 2,749 30,059 67,565 0.870 80 5620,402 38,965 63,618 0.963 70 57 33,090 66,336 109,933 1.022 60 58 — — —— Metallocene A/Activator III 130 59 4,152 16,575 32,527 0.811 120 6011,452 27,160 51,854 0.852 110 61 18,170 51,559 119,333 0.832 100 6231,274 80,916 155,858 0.819 90 63 44,361 189,479 714,702 0.775 80 6464,545 148,873 254,838 0.933 70 65 20,820 189,133 348,530 1.002

Molecular weight was observed to decrease with increasing polymerizationtemperature. Significant enhancement of Mw, for all three metallocenes,was observed when Activator III was used. Polymers made with ActivatorsI and II tended to fall in the same Mw range for each metallocene,within the temperature range tested.

Taking the DSC and GPC data together, the followingmetallocene/activator trends (1) and (2) were observed when comparisonwas made at the same polymerization temperature:Mw:C/III>A/III>C/I≧C/II>B/III>A/I≈A/II>B/I>B/II  (1)Tm:C/III>C/I≧C/II>A/III>A/I≈A/II>B/III>B/II>B/I  (2)

Depression of g′ vis with increasing Mw was observed in most GPCchromatograms, and this was taken as evidence of long chain branching.In FIG. 2, g′ f(log Mw) was compared for four of the MetalloceneA/Activator III products. All four show signatures for substantial longchain branching. Other products, such as those obtained usingMetallocene B/Activator I and Metallocene B/Activator II have g′ flogMW) plots consistent with much less LCB. All these products were madeunder relatively high propylene conversion conditions (60 to 100%) thatmay be conducive to long chain branching.

¹HNMR Results

Data from the analysis of some of the polymer products of Runs 1-65 isshown in the Table 4, below.

TABLE 4 Summary Of Olefin Populations Measured by ¹H NMR Olefin/1000 CMn × 1000 Sample Tp, ° C. Vinyl Vinylidene Vinylene ¹H NMR GPCMetallocene B/Activator I 2 90 0.25 4.42 0.08 2.95 3.59 3 80 0.13 3.140.03 4.24 5.44 4 70 0.05 2.00 0.00 6.83 8.81 5 60 0.00 1.30 0.00 10.814.24 Metallocene B/Activator II 6 60 0.04 0.52 0.00 23.2 28.4 9 80 0.240.82 0.01 10.8 1.6 12 95 0.39 2.16 0.06 5.1 1.7 15 110 0.72 4.33 0.092.7 1.3 Metallocene B/Activator III 16 120 1.09 1.39 0.01 5.53 10.0 18100 0.29 0.42 0.00 18.7 24.4 20 80 0.27 1.13 0.01 8.4 13.0 21 70 0.140.23 0.05 21.5 30.5 Metallocene C/Activator I 22 125 — — — — — 23 1200.93 1.14 0 6.76 6.69 24 115 0.51 0.82 0.09 9.86 9.82 25 110 0.78 1.210.11 6.67 9.36 26 105 — — — — — 27 100 — — — — — 28 95 0.24 0.43 0.0818.7 19.74 29 90 0.21 0.28 0.15 18.9 32.11 Metallocene C/Activator II 30130 0.99 1.11 0.01 6.1 6.0 32 110 0.46 0.40 0.01 14.4 9.0 34 90 0.170.35 0.00 23.7 25.0 Metallocene C/Activator III 36 130 0.78 0.47 0.0310.5 8.7 38 110 0.37 0.19 0.00 23.7 24.3 40 90 0.25 0.22 0.01 29.2 56.6Metallocene A/Activator I 43 130 1.58 2.18 0.06 3.66 3.12 44 120 0.851.87 0.05 5.05 — 45 110 0.49 1.55 0.07 6.64 6.13 46 100 0.26 1.12 0.049.86 — 47 90 0.12 0.82 0.04 14.29 15.59 48 80 0.05 0.48 0.04 24.56 — 4970 0.11 0.28 0.05 31.82 37.87 50 60 0.04 0.23 0.04 45.16 — MetalloceneA/Activator II 51 130 1.90 3.24 0.27 2.6 0.2 53 110 0.63 2.06 0.08 5.00.4 55 90 0.17 0.92 0.17 11.1 2.8 57 70 0.03 0.26 0.04 40.0 33.1Metallocene A/Activator III 59 130 1.67 0.31 0.02 6.4 4.2 61 110 0.500.18 0.03 19.7 18.2 63 90 0.09 0.03 0.03 82.4 44.4 65 70 0.28 0.19 0.0029.2 20.8

¹H NMR spectra were recorded for most samples. A summary of theconcentrations of the olefin unsaturations is provided in Table 4. Thenumber average molecular weight of each sample was calculated from the¹H NMR data assuming one unsaturation per chain, and in Table 4 thesevalues were compared with the number average molecular weights derivedfrom GPC. Given signal-to-noise limitations, Mn calculated from ¹H NMRis considered reasonably reliable up to about 50,000 g/mol. A parityplot of Mn (¹H NMR) versus Mn (GPC-DRI) is shown in FIG. 1. In mostcases, Mns derived from the two methods are in close agreement, althoughthere are notable exceptions. Departures from parity are thought to bedue to contributions from long chain branching.

For a given polymerization temperature, the ranking of % vinyl as afunction of metallocene-activator used is summarized in (3) below:% vinyl:A/III>C/III>B/III>C/II>C/I>A/I≧B/II˜A/II>B/I  (3)It was also observed that % vinyl generally increases, oftensubstantially, with increasing polymerization temperature for everymetallocene/activator pair examined.

All documents described herein are incorporated by reference herein,including any priority documents, related applications and/or testingprocedures to the extent they are not inconsistent with this text,provided however that any priority document not named in the initiallyfiled application or filing documents is NOT incorporated by referenceherein. As is apparent from the foregoing general description and thespecific embodiments, while forms of the invention have been illustratedand described, various modifications can be made without departing fromthe spirit and scope of the invention. Accordingly, it is not intendedthat the invention be limited thereby. Likewise, the term “comprising”is considered synonymous with the term “including” for purposes ofAustralian law. Likewise, “comprising” encompasses the terms “consistingessentially of,” “is,” and “consisting of” and any place “comprising” isused “consisting essentially of,” “is,” or “consisting of” may besubstituted therefore.

What is claimed is:
 1. A process for polymerizing olefins comprisingproviding bulky activators with a metallocene catalyst compound toadvantageously produce higher Mw, higher Tm, and/or a greater amount ofallyl chain ends of the resulting branched polyolefin than the samecatalyst with a non-bulky activator under the same polymerizationconditions and at a catalyst productivity of 4500 g/mmol or more,comprising: (i) contacting at a temperature in the range of from about35 to 150° C. one or more monomers comprising ethylene and/or propylene,with a catalyst system comprising a metallocene catalyst compound and abulky activator, wherein the metallocene catalyst compound isrepresented by the following formula:

where M is selected from the group consisting of zirconium or hafnium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines,ethers, and a combination thereof, wherein two X's optionally form apart of a fused ring or a ring system; each R¹, R², R³, R⁴, R⁵, and R⁶,is, independently, hydrogen or a substituted or unsubstitutedhydrocarbyl group, a heteroatom or heteroatom containing group; furtherprovided that any two adjacent R groups optionally form a fused ring ormulticenter fused ring system where the rings are optionally aromatic,partially saturated or saturated; further provided that any of adjacentR⁴, R⁵, and R⁶ groups optionally form a fused ring or multicenter fusedring system where the rings are optionally aromatic, partially saturatedor saturated; T is a bridging group represented by the formula R₂ _(a)J, where J is one or more of C, Si, Ge, N or P, and each R^(a) is,independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl or a C₁ to C₂₀substituted hydrocarbyl, provided that at least one R³ is a substitutedor unsubstituted phenyl group, if any of R¹, R², R⁴, R⁵, or R⁶ are nothydrogen; and wherein the bulky activator is represented by the formula:

where each R₁ is, independently, a fluoride; each R₂ is, independently,a fluoride, a C₆ to C₂₀ substituted aromatic hydrocarbyl group or asiloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group; each R₃ is a fluoride, C₆ to C₂₀substituted aromatic hydrocarbyl group or a siloxy group of the formula—O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilylgroup; wherein R₂ and R₃ can form one or more saturated or unsaturated,substituted or unsubstituted rings; L is an neutral Lewis base; (L-H)⁺is a Bronsted acid; d is 1, 2, or 3; and wherein the anion has amolecular weight of greater than 1020 g/mol; and wherein at least threeof the substituents on the B atom each have a molecular volume ofgreater than 250 cubic Å; and (ii) obtaining a branched polyolefinhaving greater than 50% allyl chain ends, relative to total unsaturatedchain ends and a Tm of 60° C. or more; wherein the molecular weight (Mw)of the branched polyolefin is adjusted to within the range of from 3000g/mole to 200,000 g/mole, and the T_(m) is adjusted to within the rangeof from 60° C. to 180° C., by the combining of bulky activators having amolecular volume of 250 cubic Å and greater.
 2. The process of claim 1,wherein step (i) occurs at a temperature greater than 35° C. and atleast 50 mol % of the monomer is converted to polyolefin.
 3. The processof claim 1, wherein the monomer is propylene.
 4. The process of claim 1,where the contacting with the catalyst system further comprisescontacting with one or more C₄ to C₄₀ alpha olefin comonomers.
 5. Theprocess of claim 4, wherein the C₄ to C₄₀ alpha olefin comonomers areselected from butene, pentene, hexene, heptene, octene, nonene, decene,cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomersthereof.
 6. The process of claim 1, wherein the catalyst system is asingle catalyst system.
 7. The process of claim 1, wherein the bulkyactivator is one or more of: trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-t-butyl-PhNMe₂H][(m-C₆F₅—C₆F₄)₄B].
 8. The process of claim 1, whereinthe process occurs in a single reaction zone.
 9. The process of claim 1,wherein alumoxane is present at 0 mol %.
 10. The process of claim 1,wherein the polymerization is a solution polymerization.
 11. The processof claim 1, wherein the residence time is up to 300 minutes.
 12. Theprocess of claim 1, wherein the metallocene is selected from(rac-dimethylsilylbis(indenyl)hafnium dimethyl,(rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl,(rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl, anddimethylrac-dimethylsilyl-bis(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)hafniumdimethyl.
 13. The process of claim 1, wherein the process is acontinuous process.
 14. The process of claim 1, wherein for themetallocene structure each R¹ is hydrogen or a methyl group, and each,R³ is hydrogen or a phenyl or substituted phenyl group, and each of R²,R⁴, R⁵, and R⁶ are hydrogen.